+

WO2009119473A1 - Pigment dispersing composition for color filters - Google Patents

Pigment dispersing composition for color filters Download PDF

Info

Publication number
WO2009119473A1
WO2009119473A1 PCT/JP2009/055584 JP2009055584W WO2009119473A1 WO 2009119473 A1 WO2009119473 A1 WO 2009119473A1 JP 2009055584 W JP2009055584 W JP 2009055584W WO 2009119473 A1 WO2009119473 A1 WO 2009119473A1
Authority
WO
WIPO (PCT)
Prior art keywords
pigment
parts
meth
acrylate
polymerizable unsaturated
Prior art date
Application number
PCT/JP2009/055584
Other languages
French (fr)
Japanese (ja)
Inventor
木下　宏司
省二 船倉
木内　栄一
嘉則 片山
Original Assignee
Dic株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Dic株式会社 filed Critical Dic株式会社
Priority to EP09726089.7A priority Critical patent/EP2209025A4/en
Priority to CN2009801003485A priority patent/CN101802660B/en
Priority to JP2009529445A priority patent/JP4423575B2/en
Priority to US12/734,567 priority patent/US8268200B2/en
Publication of WO2009119473A1 publication Critical patent/WO2009119473A1/en

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
    • C09C3/10—Treatment with macromolecular organic compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
    • C09B67/0001—Post-treatment of organic pigments or dyes
    • C09B67/0002—Grinding; Milling with solid grinding or milling assistants
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
    • C09B67/0001—Post-treatment of organic pigments or dyes
    • C09B67/0004—Coated particulate pigments or dyes
    • C09B67/0008—Coated particulate pigments or dyes with organic coatings
    • C09B67/0013—Coated particulate pigments or dyes with organic coatings with polymeric coatings
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
    • C09B67/006—Preparation of organic pigments
    • C09B67/0069—Non aqueous dispersions of pigments containing only a solvent and a dispersing agent
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
    • C09B67/0071—Process features in the making of dyestuff preparations; Dehydrating agents; Dispersing agents; Dustfree compositions
    • C09B67/0084—Dispersions of dyes
    • C09B67/0085—Non common dispersing agents
    • C09B67/009—Non common dispersing agents polymeric dispersing agent
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D17/00—Pigment pastes, e.g. for mixing in paints
    • C09D17/002—Pigment pastes, e.g. for mixing in paints in organic medium
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G02B5/22—Absorbing filters
    • G02B5/223—Absorbing filters containing organic substances, e.g. dyes, inks or pigments
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/0005—Production of optical devices or components in so far as characterised by the lithographic processes or materials used therefor
    • G03F7/0007—Filters, e.g. additive colour filters; Components for display devices
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G02B5/201—Filters in the form of arrays

Definitions

  • the present invention relates to a pigment dispersion composition for a color filter using a pigment as a coloring material.
  • the color filter is a reflective type so that the three primary colors of red, green, and blue light are selectively transmitted on a substrate provided with a mesh-like light-shielding thin film layer called a black matrix.
  • a black matrix a colored cured coating layer corresponding to each color is formed in each mesh of the black matrix so that the three primary colors of cyan, magenta, and yellow are selectively reflected, and the mesh of each color is regular.
  • the “mesh” of the black matrix is referred to as “pixel”.
  • the color filter is used for a color solid-state imaging device, a liquid crystal color display, a color display such as a color CRT.
  • color filters have also been required to have improved reliability such as color reproducibility, heat resistance, light resistance, and chemical resistance. .
  • the color filter manufacturing method was initially dyed using a dye as a colorant, but recently, pigments with excellent heat resistance, light resistance, chemical resistance, etc. have been used to meet the above requirements.
  • the pigment dispersion method has become mainstream.
  • a pigment dispersion resist in which a photopolymerizable monomer and a photopolymerization initiator are added to a pigment dispersion composition in which a pigment is dispersed using a dispersant in a binder resin is applied onto a substrate.
  • a “photolithography method” in which a cured coating layer of a pigment-dispersed resist is formed on a pixel portion by drying and exposing through a photomask, followed by development and thermosetting is generally widely performed.
  • a pigment, a coupling agent, an acrylic copolymer having an N, N-disubstituted amino group and an acidic group in the main chain or side chain As a method for producing a color filter by this “photolithography method”, for example, a pigment, a coupling agent, an acrylic copolymer having an N, N-disubstituted amino group and an acidic group in the main chain or side chain, and There has been proposed a pigment dispersion composition for a color filter which contains a solvent and is excellent in transparency, developability, light resistance and storage stability (see, for example, Patent Document 1). However, even this method is not always satisfactory with respect to the recent required properties such as higher dispersion stability, long-term storage stability, and transparency.
  • An object of the present invention is to provide a pigment dispersion composition for a color filter which uses a general-purpose pigment and is excellent in dispersion stability and storage stability.
  • the present inventor has previously invented (Japanese Patent Application No. 2006-267283), a polymer containing a polymerizable unsaturated group soluble in a non-aqueous solvent on a pigment surface and a non-aqueous solvent that is soluble and polymerized.
  • a pigment having a polymer obtained by polymerizing at least one polymerizable unsaturated monomer that becomes insoluble or hardly soluble later is dispersed when prepared as a pigment dispersion composition for a color filter
  • the present inventors have found that it is excellent in stability and have completed the present invention.
  • the present invention is a pigment dispersion composition for a color filter comprising a colorant, a resin, and an organic solvent capable of dissolving the resin, and is soluble as a colorant on the surface of the pigment (A) and in a non-aqueous solvent.
  • the pigment dispersion composition for color filters containing the modified pigment (D) which has the polymer (P) obtained by this is provided.
  • the present invention also relates to a pigment dispersion composition for a color filter comprising a colorant, a resin, and an organic solvent capable of dissolving the resin.
  • the colorant may be a pigment (A), a nonaqueous solvent, or a nonaqueous solvent.
  • At least one polymerizable unsaturated monomer (C) that is soluble in the non-aqueous solvent and insoluble or hardly soluble after polymerization in the presence of the polymer (B) containing a soluble polymerizable unsaturated group
  • a pigment dispersion composition for a color filter that uses a general-purpose pigment and is excellent in dispersion stability can be provided.
  • the modified pigment (D) used as a colorant in the present invention is a general-purpose pigment (A), a non-aqueous solvent, and a polymer (B) containing a polymerizable unsaturated group soluble in the non-aqueous solvent. It can be obtained by so-called in-situ polymerization in which at least one polymerizable unsaturated monomer (B) that is soluble in the non-aqueous solvent and becomes insoluble or hardly soluble after polymerization is polymerized. Conventionally, the in-situ polymerization method has been considered to require a polymerization field in which a pigment is finely and stably dispersed in a dispersion stabilizer.
  • a polymerizable unsaturated group soluble in a non-aqueous solvent is added.
  • the interface between the pigment (A) formed by wetting the surface of the pigment (A) with the polymer (B) contained and the polymer (B) containing a polymerizable unsaturated group soluble in a non-aqueous solvent is polymerized. It is not essential that the pigment is finely and stably dispersed in the dispersion stabilizer, and therefore surface treatment of the pigment to form a finely dispersed state is not always necessary, and a wide range of It can be applied to various types of pigments.
  • the pigment (A) used in the present invention is at least one pigment selected from known and commonly used organic pigments or inorganic pigments. In the present invention, either an untreated pigment or a treated pigment can be applied.
  • pigment (A) commercially available pigments conventionally used for color filters, and “Color Index Handbook” (edited by the Japan Pigment Technical Association, published in 1977) “Latest Pigment Applied Technology” (CMC Publishing, 1986) “Printing Ink Technology” (CMC Publishing Co., Ltd. published in 1984) and the like.
  • a pigment generally used in color filters for example, C.I. I. Pigment red 254 and C.I. I. Pigment red 177 and C.I. I. Red pigments such as CI Pigment Orange 71; I. Pigment green 36, C.I. I. Pigment green 58 and C.I. I. Pigment Green 7 and other green pigments, C.I. I. Pigment blue 15: 6 and C.I.
  • I. Blue pigments such as CI Pigment Blue 22; I. Pigment violet 23 and C.I. I. Violet pigments such as CI Pigment Violet 50, C.I. I. Pigment yellow 138, C.I. I. Pigment yellow 150 and C.I. I. Yellow pigments such as CI Pigment Yellow 20 and the like; I. Examples thereof include CI pigment black 7, black pigments such as carbon black and titanium black, and these pigments can be used alone or in combination of two or more as required.
  • the transparency of a cured coating film of a pigment dispersion for a color filter increases as the particle diameter of the pigment contained decreases, but the primary particle diameter is preferably in the range of 10 to 80 nm, preferably 30 to 50 nm. The range is particularly preferable. If the primary particle diameter is less than 10 nm, the cohesiveness of the pigment becomes high, making it difficult to disperse, and if it exceeds 80 nm, the transparency is lowered.
  • Non-aqueous solvent used in the present invention is an organic solvent in which an aliphatic and / or alicyclic hydrocarbon solvent is essential.
  • examples of the aliphatic and / or alicyclic hydrocarbon solvents include n-hexane, n-heptane, n-octane, “Loose” or “Mineral Split EC” of Shell Chemicals, and ExxonMobil Chemical.
  • organic solvents include “Swazole 100 or 150” manufactured by Maruzen Petrochemical Co., Ltd., aromatic hydrocarbon solvents such as toluene or xylene; methyl acetate, ethyl acetate, acetic acid- esters such as n-butyl or amyl acetate; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, methyl amyl ketone or cyclohexanone; or such as methanol, ethanol, n-propanol, i-propanol or n-butanol Examples include alcohols.
  • the amount of the aliphatic and / or alicyclic hydrocarbon solvent used is preferably 50% by mass or more, and more preferably 60% by mass or more.
  • the polymer (B) containing a polymerizable unsaturated group soluble in a nonaqueous solvent used in the present invention is mainly an alkyl (meth) acrylate having an alkyl group having 4 or more carbon atoms.
  • Polymerization mainly comprising a polymer having a polymerizable unsaturated group introduced into a copolymer of a polymerizable unsaturated monomer as a component, or an alkyl (meth) acrylate having an alkyl group having 4 or more carbon atoms This term refers to a macromonomer composed of a copolymer of unsaturated monomers.
  • alkyl (meth) acrylate having an alkyl group having 4 or more carbon atoms examples include n-butyl (meth) acrylate, i-butyl (meth) acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meta ) Acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, isostearyl (meth) acrylate, cyclohexyl (meth) acrylate, and the like.
  • Polymerizable unsaturated monomers other than alkyl (meth) acrylates that can be used include aromatic vinyl monomers such as styrene, ⁇ -methylstyrene, pt-butylstyrene or vinyltoluene, benzyl ( (Meth) acrylate, dimethylamino (meth) acrylate, diethylamino (meth) acrylate, (meth) acrylates such as dibromopropyl (meth) acrylate or tribromophenyl (meth) acrylate, maleic acid, fumaric acid or itaconic acid, etc.
  • aromatic vinyl monomers such as styrene, ⁇ -methylstyrene, pt-butylstyrene or vinyltoluene
  • benzyl ( (Meth) acrylate dimethylamino (meth) acrylate, diethylamino (meth) acrylate
  • a single polymer of a polymerizable unsaturated group-containing monomer that can be used other than these alkyl (meth) acrylates has low solubility in the non-aqueous medium, so it is used as an alkyl (meth) acrylate and a random polymer. It is preferred that When the copolymerization is carried out in the form of a block or a graft, the solubility in the non-aqueous medium is remarkably lowered, which is not preferable.
  • polymerizable unsaturated monomers may be used alone or in combination of two or more.
  • linear or branched alkyl (meth) acrylates having an alkyl group of 4 to 12 carbon atoms such as n-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl methacrylate and the like is particularly preferable.
  • a copolymer of a polymerizable unsaturated monomer having an alkyl (meth) acrylate having an alkyl group having 4 or more carbon atoms as a main component is obtained by polymerizing the polymerizable unsaturated monomer by a conventional method. can get.
  • polymerizable unsaturated A polymer (B) containing groups is obtained.
  • a method for introducing a polymerizable unsaturated group for example, a carboxyl group-containing polymerizable monomer such as acrylic acid or methacrylic acid or an amino group such as dimethylaminoethyl methacrylate or dimethylaminopropylacrylamide is previously used as the copolymer component.
  • a polymerizable monomer is blended and copolymerized to obtain the copolymer having a carboxyl group or an amino group, and then having the carboxyl group or amino group, a glycidyl group such as glycidyl methacrylate, and a polymerizable unsaturated group.
  • a method of reacting monomers A hydroxyl group-containing monomer such as 2-hydroxyethyl methacrylate or 2-hydroxyethyl acrylate is previously blended and copolymerized as the copolymer component to obtain the copolymer having a hydroxyl group, and then the hydroxyl group and isocyanate ethyl methacrylate are obtained.
  • an isocyanate group such as During polymerization, thioglycolic acid is used as a chain transfer agent to introduce a carboxyl group at the end of the copolymer, and a monomer having a glycidyl group such as glycidyl methacrylate and a polymerizable unsaturated group is added to the carboxyl group.
  • a carboxyl group-containing azo initiator such as azobiscyanopentanoic acid is used to introduce a carboxyl group into the copolymer, and a glycidyl group such as glycidyl methacrylate and a polymerizable unsaturated group are introduced into the carboxyl group.
  • a carboxyl group-containing monomer such as acrylic acid or methacrylic acid or an amino group-containing monomer such as dimethylaminoethyl methacrylate or dimethylaminopropylacrylamide is copolymerized, and the carboxyl group or amino group and glycidyl methacrylate are copolymerized.
  • a method of reacting a monomer having a polymerizable unsaturated group with a glycidyl group such as the simplest is preferable.
  • the polymerizable unsaturated monomer (C) used in the present invention that is soluble in the non-aqueous solvent and becomes insoluble or hardly soluble after polymerization is specifically exemplified by methyl (meth) acrylate, ethyl ( Such as olefins such as (meth) acrylate, n-propyl (meth) acrylate or i-propyl (meth) acrylate, or (meth) acrylonitrile, vinyl acetate, vinyl chloride, vinylidene chloride, vinyl fluoride or vinylidene fluoride, Vinyl monomers having no so-called reactive polar groups (functional groups); (meth) acrylamide, dimethyl (meth) acrylamide, Nt-butyl (meth) acrylamide, N-octyl (meth) acryl
  • Epoxy group-containing polymerizable unsaturated monomers such as epoxy group-containing polymerizable compounds obtained by addition reaction of various polyepoxy compounds having a poxy group at an equimolar ratio; 2-hydroxyethyl (meth) acrylate-hexa Isocyanate group-containing ⁇ , ⁇ -ethylenically unsaturated mono
  • ⁇ -Unsaturated carboxylic acid hydroalkyl esters of maleic acid, succinic acid, phthalic acid, hexahydrophthalic acid, tetrahydrophthalic acid, benzenetricarboxylic acid, benzenetetracarboxylic acid, "hymic acid”, tetrachlorophthalic acid or dodecynyl succinic acid Carboxyl group-containing ⁇ , ⁇ -ethylenically unsaturated monomers such as adducts of polycarboxylic acid anhydrides and the like.
  • C3 or lower alkyl (meth) acrylates such as methyl (meth) acrylate and ethyl (meth) acrylate is preferred.
  • the polymer is crosslinked.
  • the polyfunctional polymerizable unsaturated monomer used as the crosslinking component include divinylbenzene, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, polyethylene glycol di ( (Meth) acrylate, 1,3-butanediol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol dimethacrylate, trimethylolpropane tri Ethoxytri (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaeryth
  • a polymer having an essential component of a polymerizable unsaturated monomer (C) which is soluble in at least one non-aqueous solvent and becomes insoluble or hardly soluble after polymerization is not dissolved in the non-aqueous solvent system.
  • Other polymerizable unsaturated monomers may be used.
  • examples of other polymerizable unsaturated monomers include polymerizable unsaturated monomers that can be used other than the alkyl (meth) acrylate having an alkyl group having 4 or more carbon atoms and the alkyl (meth) acrylate described above. A monomer is mentioned.
  • the modified pigment (D) used in the present invention contains a pigment (A), a non-aqueous solvent, and a polymer (B) containing a polymerizable unsaturated group soluble in the non-aqueous solvent. It is obtained by polymerizing at least one polymerizable unsaturated monomer (C) that is soluble and insoluble or hardly soluble after polymerization.
  • the pigment (A) and the polymer (B) containing a polymerizable unsaturated group soluble in a non-aqueous solvent are preferably mixed before polymerization.
  • a homogenizer for example, a homogenizer, a disper, a bead mill, a paint shaker, a kneader, a roll mill, a ball mill, an attritor, a sand mill and the like can be used.
  • the form of the pigment to be used is not limited, and any form of slurry, wet cake, and powder may be used. That is, in the production method of the present invention, even a pigment containing water such as a wet cake can be used.
  • the polymerizable unsaturated monomer (C) and a polymerization initiator described later are further mixed and polymerized to obtain the modified pigment (D).
  • the amount of the polymer (B) used is not particularly limited because it is appropriately optimized depending on the purpose, but usually 1 to 200 parts are used, more preferably 100 parts of the pigment (A). 5 to 50 parts, more preferably 5 to 30 parts.
  • the amount of the polymerizable unsaturated monomer (C) used is also not particularly limited since it is appropriately optimized depending on the purpose, but usually 1 to 200 parts per 100 parts of the pigment (A). More preferably 5 to 50 parts, still more preferably 5 to 30 parts.
  • the amount of the polymer (P) finally coated on the pigment is preferably 2 to 400 parts, more preferably 10 to 100 parts, still more preferably 10 to 60 parts per 100 parts of the pigment (A). Part. At that time, it is preferable to use at least one polymerizable unsaturated monomer (C) in a proportion of usually 10 to 400 parts, preferably 30 to 400 parts, per 100 parts of the polymer (B). Parts, more preferably 50 to 200 parts.
  • a method of polymerizing the polymerizable unsaturated monomer (C) in the presence of the pigment (A), the non-aqueous solvent, and the polymer (B) may be performed by a known and conventional polymerization method. Usually, it is carried out in the presence of a polymerization initiator.
  • Such polymerization initiators include azobisisobutyronitrile (AIBN), 2,2-azobis (2-methylbutyronitrile), benzoyl peroxide, t-butyl perbenzoate, t-butyl-2-ethylhexano
  • AIBN azobisisobutyronitrile
  • 2,2-azobis (2-methylbutyronitrile) 2,2-azobis (2-methylbutyronitrile
  • benzoyl peroxide t-butyl perbenzoate
  • a radical generating polymerization catalyst such as ate, t-butyl hydroperoxide, di-t-butyl peroxide, or cumene hydroperoxide is used alone or in combination of two or more.
  • a method in which the polymerization initiator is dissolved in the polymerizable unsaturated monomer (C) and added to the mixed system of the pigment (A) and the polymer (B) is preferable.
  • the polymerizable unsaturated monomer (C) or the polymerizable unsaturated monomer (C) in which the polymerization initiator is dissolved can be added by a dropping method in a state where the polymerization temperature is reached.
  • a method of adding the polymer at a normal temperature before warming, heating the polymer after sufficiently mixing, and polymerizing is stable and preferable.
  • the polymerization temperature is usually in the range of 60 ° C to 130 ° C.
  • the pigment (A) is an organic pigment, if the polymerization temperature is too high, the pigment may undergo significant changes in shape such as alteration or crystal growth. In such a case, it is preferable to polymerize at 70 to 100 ° C.
  • the non-aqueous solvent used for the polymerization is removed by filtration, followed by drying and pulverization to obtain a powdery polymer-coated pigment.
  • Nutsche, filter press, etc. can be used for the filtration method.
  • it can dry with well-known drying apparatuses, such as a box-type dryer, a vacuum dryer, a band dryer, and a spray dryer.
  • a known pulverizer such as a mortar, a hammer mill, a disk mill, a pin mill, or a jet mill can be used.
  • the pigment dispersion composition for a color filter of the present invention can be obtained by dispersing the modified pigment (D) in a resin solution in which a pigment dispersant such as a resin and an organic solvent are mixed.
  • a publicly known and commonly used pigment dispersion method can be used, and the pigment dispersion is performed using a dispersing machine such as a ball mill, a sand mill, a bead mill, a three-roll mill, a paint conditioner, an attritor, a dispersion stirrer, or an ultrasonic wave.
  • a dispersing machine such as a ball mill, a sand mill, a bead mill, a three-roll mill, a paint conditioner, an attritor, a dispersion stirrer, or an ultrasonic wave. I can do things.
  • Specific dispersing equipment includes super apex mill (manufactured by Kotobuki Giken Kogyo Co., Ltd.), ultra apex mill (manufactured by Kotobuki Giken Kogyo Co., Ltd.), dry swerke PM-DCP stirring bead mill device (manufactured by dry swerke), pico glen mill ( Asada Iron Works Co., Ltd.).
  • the grinding medium used for pigment dispersion examples include a zirconia or steel grinding medium, and among these, a zirconia grinding medium having excellent wear resistance is particularly preferable.
  • the diameter of the grinding mediator is preferably in the range of 0.01 to 3.0 mm, particularly preferably in the range of 0.05 to 0.5 mm. When the diameter of the grinding medium is larger than 3.0 mm, the wet pulverization becomes insufficient, which is not preferable.
  • pigment dispersant used in the pigment dispersion a known pigment dispersant generally used for pigment dispersion can be used.
  • examples include surfactants, pigment intermediates or derivatives, dye intermediates or derivatives, or resin-type dispersants such as polyamide resins, polyurethane resins, polyester resins, and acrylic resins.
  • resin-type dispersants such as polyamide resins, polyurethane resins, polyester resins, and acrylic resins.
  • resin-type dispersants include, for example, “DISPERBYK-130”, “DISPERBYK-161”, “DISPERBYK-162”, “DISPERBYK-163”, “DISPERBYK-170”, “DISPERBYK-171” manufactured by BYK Chemie.
  • organic solvent used for pigment dispersion examples include aromatic solvents such as toluene, xylene and methoxybenzene, ethyl acetate, propyl acetate and butyl acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate and the like.
  • Acetic acid ester solvents propionate solvents such as ethoxyethyl propionate, alcohol solvents such as methanol and ethanol, ether solvents such as butyl cellosolve, propylene glycol monomethyl ether, diethylene glycol ethyl ether, diethylene glycol dimethyl ether, methyl ethyl ketone, methyl isobutyl ketone, Ketone solvents such as cyclohexanone, aliphatic hydrocarbon solvents such as hexane, N, N-dimethylformamide, ⁇ -butyrolas Nitride-based solvents such as Tam, N-methyl-2-pyrrolidone, aniline and pyridine, lactone-based solvents such as ⁇ -butyrolactone, carbamate esters such as a 48:52 mixture of methyl carbamate and ethyl carbamate, water Etc.
  • ether solvents such as butyl cellosolve
  • water-soluble polar solvents such as propionate, alcohol, ether, ketone, nitrogen compound, and lactone are particularly preferable.
  • water-soluble organic solvent water can be used in combination.
  • these solvents can also use 2 or more types together.
  • each there is no particular limitation on the use ratio of each, generally 5 to 200 parts of pigment dispersant, preferably 10 to 100 pigment dispersant, more preferably 100 parts of the modified pigment (D). 10 to 60 pigment dispersant is used, and the organic solvent is used so that the total solid content of the modified pigment (D) and the pigment dispersant is 10 to 25%, preferably 10 to 20%.
  • the pigment dispersion composition for a color filter of the present invention can be used for producing a color filter having red, green and blue color pixel portions and a black matrix.
  • any known and commonly used production methods such as a photolithography method, an ink jet method, and a printing method can be employed.
  • a photolithography method uses a photocurable composition in which a photocurable monomer or oligomer, a photopolymerization initiator, or the like is appropriately mixed with the pigment dispersion composition for a color filter of the present invention, and a black matrix of a transparent substrate for a color filter.
  • pattern exposure is performed by irradiating ultraviolet rays or visible light in the wavelength range of 200 to 500 nm through a photomask, and the portions corresponding to the pixel portions are exposed.
  • the photocurable compound is cured, and then the unexposed portion is developed with a developer, the non-pixel portion is removed, and the pixel portion is fixed to the transparent substrate.
  • a pixel portion made of a cured colored film of a photocurable composition is formed on a transparent substrate.
  • a photocurable composition is prepared for each of the black, red, green, and blue modified pigments (D), and the above-described operation is repeated to form a black matrix.
  • red, green, and blue are formed at predetermined positions.
  • a color filter having each color pixel portion can be manufactured.
  • yellow modified pigment (D) or purple modified pigment (D) can be used in combination for the formation of red, green and blue pixel portions. If necessary, the entire color filter after photocuring can be heat-treated (post-baked).
  • Examples of the method for applying the photocurable composition onto a transparent substrate such as glass include a spin coating method, a roll coating method, and an inkjet method.
  • the heat drying conditions of the photocurable composition after coating vary depending on the type of each component, the blending ratio, etc., but is usually 50 to 150 ° C. for about 1 to 15 minutes.
  • Examples of the developing method after pattern exposure include a liquid piling method, a dipping method, and a spray method.
  • the transparent substrate on which the necessary color pixel portions are formed is washed with water and dried. The color filter thus obtained is subjected to a heat treatment (post-baking) at 100 to 280 ° C.
  • a heating device such as a hot plate or an oven to remove volatile components in the coating film and at the same time photo-curing.
  • the unreacted photocurable compound remaining in the cured colored film of the curable composition is thermally cured to complete the color filter.
  • the color filter using the pigment dispersion composition for a color filter of the present invention is not limited to the method, for example, an electrodeposition method, You may manufacture by methods, such as a transcription
  • reaction solution was lowered to 50 ° C., a solution in which 0.2 part of t-butylpyrocatechol was dissolved in 15 parts of butyl acetate was added, and 15 parts of glycidyl methacrylate and 30 parts of dimethylaminoethanol were further added.
  • the mixture was heated to 80 ° C. and reacted at the same temperature for 10 hours to obtain a polymer (B-1) solution containing a polymerizable unsaturated group soluble in a non-aqueous solvent.
  • Reference Example 2 Synthesis of Polymer (B-2) Containing Polymerizable Unsaturated Group Soluble in Nonaqueous Solvent
  • 500 parts of heptane and 500 parts of butyl acetate were charged and the temperature was raised to 90 ° C.
  • 950 parts of butyl acrylate and dimethylaminoethyl methacrylate were added.
  • a mixture consisting of 50 parts and 7 parts of 2,2′-azobis (2-methylbutyronitrile) was added dropwise over 5 hours. After completion of the addition, the reaction was continued for 10 hours at the same temperature.
  • the temperature of the reaction solution was lowered to 50 ° C., a solution in which 0.2 part of t-butylpyrocatechol was dissolved in 20 parts of butyl acetate was added, 20 parts of glycidyl methacrylate was further added, and the temperature was raised to 80 ° C.
  • a polymer (B-2) solution containing a polymerizable unsaturated group soluble in a non-aqueous solvent was obtained.
  • ⁇ Reference Example 4 Synthesis of Modified Pigment (D-2)> 208 parts of the ⁇ -type copper phthalocyanine blue wet cake (pigment content 48%) obtained in Reference Example 3, 15 parts of the polymer (B-1) obtained in Reference Example 1, 600 parts of 1.25 mm zirconia beads 300 parts of heptane were put into a polyethylene jar and mixed for 90 minutes with a paint shaker (Toyo Seiki Co., Ltd.). After dilution with 300 parts of heptane, the zirconia beads were removed to prepare a pigment mixture.
  • the polymer-treated pigment and the polymerization solvent were separated by filtration.
  • the obtained polymer-treated pigment was dried with a hot air dryer at 100 ° C. for 5 hours and then pulverized with a pulverizer to obtain a modified pigment (D-3).
  • ⁇ Reference Example 6 Synthesis of Modified Pigment (D-4)> 200 parts of polybrominated zinc phthalocyanine having an average primary particle size of 0.1 to 10 ⁇ m, 2000 parts of crushed sodium chloride, and 200 parts of diethylene glycol were charged into a double-arm kneader and kneaded at 100 ° C. for 8 hours. After completion of the kneading, the pigment component of polybrominated zinc phthalocyanine (CI Pigment Green 58) is obtained by taking out into warm water of 60 ° C., stirring for 1 hour, repeating filtration and washing with hot water, and then performing press filtration. A 45% wet cake was obtained.
  • CI Pigment Green 58 the pigment component of polybrominated zinc phthalocyanine
  • the average particle size of the primary particles measured with a transmission electron microscope JEM-2010 was 50 nm.
  • 222 parts of the resulting polybrominated zinc phthalocyanine wet cake, 10 parts of the polymer (B-2) obtained in Reference Example 2, 600 parts of 1.25 mm zirconia beads and 300 parts of heptane were placed in a polyethylene jar. And mixed for 60 minutes with a paint shaker (Toyo Seiki Co., Ltd.). After dilution with 300 parts of heptane, the zirconia beads were removed to prepare a pigment mixture.
  • the polymer-treated pigment and the polymerization solvent were separated by filtration.
  • the obtained polymer-treated pigment was dried with a hot air dryer at 100 ° C. for 5 hours and then pulverized with a pulverizer to obtain a modified pigment (D-6).
  • the polymer-treated pigment and the polymerization solvent were separated by filtration.
  • the obtained polymer-treated pigment was dried with a hot air dryer at 100 ° C. for 5 hours and then pulverized with a pulverizer to obtain a modified pigment (D-7).
  • Example 1 9 parts of the modified pigment (D-1) obtained in Reference Example 3, 0.5 part of copper phthalocyanine monophthalimidomethyl (phthalocyanine derivative) and 0.5 part of copper phthalocyanine monosulfonic acid (phthalocyanine derivative) as a dispersion aid, Add 5 parts of Azisper PB814 (Ajinomoto Fine Techno Pigment Dispersant, active ingredient 60%), 57.2 parts of propylene glycol monomethyl ether acetate, 0.3 mm ⁇ Sepul beads, and disperse for 3 hours with Paint Conditioner (Toyo Seiki Co., Ltd.) Then, the pigment dispersion composition was obtained by removing 0.3 mm ⁇ sepul beads.
  • the viscosity of the pigment dispersion was 10 mPa ⁇ s on a RE550L viscometer manufactured by Toki Sangyo under the conditions of 20 ° C. and 10 rpm. Moreover, the viscosity after storage for 1 week at 40 ° C. was a pigment dispersion composition having a high dispersion stability with no change at 10 mPa ⁇ s and no precipitation of the pigment. About the viscosity change, the viscosity change within ⁇ 10% was regarded as acceptable.
  • Examples 2 to 7 A pigment dispersion composition was prepared in the same manner as in Example 1 except that the modified pigment (D-1), derivative, solvent, and pigment dispersant used were changed as described in Tables 1 and 2, and the viscosity and storage were prepared. Stability was evaluated.
  • ⁇ Comparative Example 1 10 parts of Fast Gen Green 2YK-CF (Dainippon Ink Chemical Co., Ltd. polyhalogenated copper phthalocyanine pigment, CI Pigment Green 36) (the pigment used in the modified pigment (D-3)), Add 10 parts of Azisper PB814 (Ajinomoto Fine Techno Pigment Dispersant, active ingredient 60%), 55.2 parts of propylene glycol monomethyl ether acetate, 0.3 mm ⁇ Sepul beads, and disperse for 3 hours with Paint Conditioner (Toyo Seiki Co., Ltd.) Then, the pigment dispersion composition was obtained by removing 0.3 mm ⁇ sepul beads.
  • the viscosity of the pigment dispersion was 11 mPa ⁇ s using a RE550L viscometer manufactured by Toki Sangyo under the conditions of 20 ° C. and 10 rpm. However, the viscosity after storage at 40 ° C. for 1 week was increased at 24 mPa ⁇ s, and precipitation of the pigment was also observed. The viscosity change was rejected because it was not within ⁇ 10%.
  • a pigment dispersion composition was prepared in the same manner as in Example 1 except that the pigment, solvent, and pigment dispersant used were changed to those shown in Table 2, and the viscosity and storage stability were evaluated.
  • Phthalocyanine derivative 1 is “copper phthalocyanine monophthalimidomethyl (dispersing aid)”
  • Phthalocyanine derivative 2 is “copper phthalocyanine monosulfonic acid (dispersion aid)”
  • Azisper PB814" is “Ajinomoto Fine Techno pigment dispersant, active ingredient 60%”
  • DISPERBYK-2001 is “pigment dispersant by BYK, active ingredient 46%”
  • PGMEA is “propylene glycol monomethyl ether acetate”.
  • Pigment 1 is “Fastgen Green 2YK-CF (Dainippon Ink Chemical Co., Ltd. polyhalogenated copper phthalocyanine pigment, CI Pigment Green 36)”
  • Pigment 2 is “Hostaperm Violet RL-NF (product of Clariant, CI Pigment Violet 23)”
  • Azisper PB814 is “Ajinomoto Fine Techno Pigment Dispersant, Active ingredient 60%”
  • DISPERBYK-2001 is “pigment dispersant by BYK, active ingredient 46%”
  • PGMEA is “propylene glycol monomethyl ether acetate”.
  • Comparative Example 1 is an example in which the unmodified pigment (D-3) used in Example 3 was used, but the viscosity change was large and the pigment settled.
  • Comparative Example 2 is an example in which the unmodified pigment of the modified pigment (D-6) used in Example 6 was used. This also showed a large change in viscosity, and precipitation of the pigment was also observed.
  • the pigment dispersion composition for color filters of the present invention using the modified pigments (D-1) to (D-7) showed stable dispersibility regardless of the type of pigment used.
  • the color resist was applied to 1 mm thick glass using a spin coater so as to have a dry film thickness of 1 ⁇ m, and then preliminarily dried at 60 ° C. for 5 minutes to form a coating film. After exposure with ultraviolet rays, the coating film was cured by heat treatment at 230 ° C. for 15 minutes to obtain a color filter. Contrast is measured when the color filter is installed between two polarizing plates, a light source is installed on one side, and a CCD camera is installed on the other side. It was calculated from the ratio of brightness (transmitted light intensity) to time. As a result, the contrast of the obtained color filter was 5900.
  • ⁇ Application example 2 75 parts of the pigment dispersion composition obtained in Example 4, 5.5 parts of a polyester acrylate resin (Aronix (trade name) M7100, manufactured by Toa Gosei Chemical Co., Ltd.), dipentaerythrate hexaacrylate (KAYARAD (trademark) Name) DPHA (made by Nippon Kayaku Co., Ltd.) 5 parts, benzophenone (KAYACURE (trade name) BP-100, made by Nippon Kayaku Co., Ltd.) 1 part, Euker ester EFP 13.5 parts are stirred with a dispersion stirrer, and the pore size is 1 Filtration through a 0.0 ⁇ m filter gave a color resist.
  • a polyester acrylate resin Aronix (trade name) M7100, manufactured by Toa Gosei Chemical Co., Ltd.
  • dipentaerythrate hexaacrylate DPHA (made by Nippon Kayaku Co., Ltd.) 5 parts
  • benzophenone
  • the color resist was applied to 1 mm thick glass using a spin coater so as to have a dry film thickness of 1 ⁇ m, and then preliminarily dried at 60 ° C. for 5 minutes to form a coating film. After exposure with ultraviolet rays, the coating film was cured by heat treatment at 230 ° C. for 15 minutes to obtain a color filter. As a result of measuring the contrast of the obtained color filter in the same manner as in Application Example 1, it was 8800.
  • the pigment dispersion composition for a color filter has high stability, and a color filter produced using these has a high contrast and can be used for production of a high-performance color filter.
  • the pigment dispersion composition for a color filter of the present invention can be used for applications such as printing ink, paint, colored resin molded product, electrostatic charge image developing toner, ink jet recording ink and the like.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Materials Engineering (AREA)
  • Dispersion Chemistry (AREA)
  • Nanotechnology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Composite Materials (AREA)
  • Optics & Photonics (AREA)
  • Wood Science & Technology (AREA)
  • Pigments, Carbon Blacks, Or Wood Stains (AREA)
  • Macromonomer-Based Addition Polymer (AREA)
  • Optical Filters (AREA)
  • Paints Or Removers (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

Provided is a pigment dispersing composition for color filters, which comprises a colorant, a resin, and an organic solvent that can dissolve the resin, wherein the colorant is a modified pigment (D) having, on the surface of a pigment (A), a polymer (P) obtained by polymerizing a polymer (B), which contains a polymerizable unsaturated group and is soluble in a non-aqueous solvent, and at least one type of polymerizable unsaturated monomer (C), which is soluble in a non-aqueous solvent and becomes insoluble or poorly soluble after polymerization. Alternatively provided is a pigment dispersing composition for color filters, which contains a colorant, a resin, and an organic solvent that can dissolve the resin, wherein the colorant is a modified pigment (D) obtained by polymerizing-in the presence of a pigment (A), a non-aqueous solvent, and a polymer (B) which contains a polymerizable unsaturated group and is soluble in the non-aqueous solvent-at least one type of polymerizable unsaturated monomer (C) which is soluble in the non-aqueous solvent and becomes insoluble or poorly soluble after polymerization.

Description

カラーフィルター用顔料分散組成物Pigment dispersion composition for color filter
　本発明は、色材として顔料を使用したカラーフィルター用顔料分散組成物に関する。 The present invention relates to a pigment dispersion composition for a color filter using a pigment as a coloring material.
　一般にカラーフィルターは、ブラックマトリックスと呼ばれる網目状の遮光薄膜層を設けた基板上に、透過型の場合はレッド、グリーン、ブルーの光の３原色を選択的に透過するように、反射型の場合にはシアン、マゼンタ、イエローの色の３原色を選択的に反射するように、ブラックマトリックスの各網目の中に各色に相当する着色硬化塗膜層を形成し、かつ、この各色の網目が規則的に配列されている。なお、上記ブラックマトリックスの「網目」は「画素」と称される。 In general, the color filter is a reflective type so that the three primary colors of red, green, and blue light are selectively transmitted on a substrate provided with a mesh-like light-shielding thin film layer called a black matrix. In the black matrix, a colored cured coating layer corresponding to each color is formed in each mesh of the black matrix so that the three primary colors of cyan, magenta, and yellow are selectively reflected, and the mesh of each color is regular. Are arranged. The “mesh” of the black matrix is referred to as “pixel”.
　カラーフィルターは、カラー個体撮像素子や、液晶カラーディスプレイ、カラーＣＲＴ等のカラーディスプレイに使用されている。近年、カラー液晶ディスプレイパネルの大型化、用途の多様化に伴い、カラーフィルターにも、色再現性、耐熱性、耐光性、耐薬品性等の信頼性向上がより要求されるようになってきた。 The color filter is used for a color solid-state imaging device, a liquid crystal color display, a color display such as a color CRT. In recent years, as color liquid crystal display panels have become larger and diversified in use, color filters have also been required to have improved reliability such as color reproducibility, heat resistance, light resistance, and chemical resistance. .
　カラーフィルターの製造方法は、初期においては着色剤として染料を使用する染色法が主流であったが、上記要求に対応するため、最近では耐熱性、耐光性、耐薬品性等に優れる顔料を使用した顔料分散法が主流となっている。この顔料分散法においては、バインダー樹脂中に分散剤を用いて顔料を分散させた顔料分散組成物に、光重合性モノマー、光重合開始剤を添加した顔料分散レジストを基材上に塗布して乾燥させ、フォトマスクを通して露光した後、現像及び熱硬化処理を行うことによって、画素部に顔料分散レジストの硬化塗膜層を形成する「フォトリソグラフィー法」が一般的に広く行われている。 The color filter manufacturing method was initially dyed using a dye as a colorant, but recently, pigments with excellent heat resistance, light resistance, chemical resistance, etc. have been used to meet the above requirements. The pigment dispersion method has become mainstream. In this pigment dispersion method, a pigment dispersion resist in which a photopolymerizable monomer and a photopolymerization initiator are added to a pigment dispersion composition in which a pigment is dispersed using a dispersant in a binder resin is applied onto a substrate. A “photolithography method” in which a cured coating layer of a pigment-dispersed resist is formed on a pixel portion by drying and exposing through a photomask, followed by development and thermosetting is generally widely performed.
　この「フォトリソグラフィー法」によってカラーフィルターを製造する方法としては、例えば、顔料、カップリング剤、主鎖又は側鎖にＮ，Ｎ－ジ置換アミノ基及び酸性基を有するアクリル系共重合体、及び溶剤を含有させて、透明性、現像性、耐光性に優れ、かつ保存安定性に優れたカラーフィルター用顔料分散組成物が提案されている（例えば、特許文献１参照）。しかしながら該方法においても、近年のより高い分散安定性や長期保存安定性、透明性等についての要求特性に対しては、必ずしも十分に満足できるものではない。 As a method for producing a color filter by this “photolithography method”, for example, a pigment, a coupling agent, an acrylic copolymer having an N, N-disubstituted amino group and an acidic group in the main chain or side chain, and There has been proposed a pigment dispersion composition for a color filter which contains a solvent and is excellent in transparency, developability, light resistance and storage stability (see, for example, Patent Document 1). However, even this method is not always satisfactory with respect to the recent required properties such as higher dispersion stability, long-term storage stability, and transparency.
これに対し、汎用の顔料と樹脂と有機溶剤とを原料として混練するに際し、該顔料と該樹脂との固形分比率（質量換算）を特定比率とし、且つ該有機溶剤を蒸発させて除去しながら該原料をプラネタリーミキサーによって混練することにより、分散安定性や長期保存安定性、透明性等に優れたカラーフィルター用顔料分散液を得る方法が知られている。（例えば特許文献２参照）。しかしながら該方法は、固形分比率を常にモニタリングしながら混練することや、固練りであるために長時間の混練を必要し、簡便な混練方法とはいえない。
特開２００３－６４２９３号公報（段落［０００２］～［０００８］） 特開２００６－１１１７５２号公報 In contrast, when kneading a general-purpose pigment, resin, and organic solvent as raw materials, the solid content ratio (in terms of mass) of the pigment and the resin is set to a specific ratio, and the organic solvent is removed by evaporation. There is known a method of obtaining a pigment dispersion for a color filter excellent in dispersion stability, long-term storage stability, transparency, and the like by kneading the raw materials with a planetary mixer. (For example, refer to Patent Document 2). However, this method is not a simple kneading method because it involves kneading while constantly monitoring the solid content ratio, or requires kneading for a long time because it is solid kneading.
JP 2003-64293 A (paragraphs [0002] to [0008]) JP 2006-111752 A
　本発明の課題は、汎用の顔料を使用し、分散安定性、保存安定性に優れるカラーフィルター用顔料分散組成物を提供することにある。 An object of the present invention is to provide a pigment dispersion composition for a color filter which uses a general-purpose pigment and is excellent in dispersion stability and storage stability.
　本発明者は、先に発明した（特願２００６－２６７２８３号公報）、顔料表面に、非水溶媒に可溶な重合性不飽和基を含有するポリマーと非水溶媒に可溶でありかつ重合後に不溶もしくは難溶になる少なくとも１種の重合性不飽和単量体とを重合することにより得られるポリマーを有することを特徴とする顔料が、カラーフィルター用顔料分散組成物として調整したときに分散安定性に優れることを見出し、本発明を完成するに至った。 The present inventor has previously invented (Japanese Patent Application No. 2006-267283), a polymer containing a polymerizable unsaturated group soluble in a non-aqueous solvent on a pigment surface and a non-aqueous solvent that is soluble and polymerized. A pigment having a polymer obtained by polymerizing at least one polymerizable unsaturated monomer that becomes insoluble or hardly soluble later is dispersed when prepared as a pigment dispersion composition for a color filter The present inventors have found that it is excellent in stability and have completed the present invention.
　即ち、本発明は、色剤と樹脂と該樹脂を溶解し得る有機溶剤とから成るカラーフィルター用顔料分散組成物であって、色剤として、顔料（Ａ）表面に、非水溶媒に可溶な重合性不飽和基を含有するポリマー（Ｂ）と非水溶媒に可溶でありかつ重合後に不溶もしくは難溶になる少なくとも１種の重合性不飽和単量体（Ｃ）とを重合することにより得られるポリマー（Ｐ）を有する変性顔料（Ｄ）を含有するカラーフィルター用顔料分散組成物を提供する。 That is, the present invention is a pigment dispersion composition for a color filter comprising a colorant, a resin, and an organic solvent capable of dissolving the resin, and is soluble as a colorant on the surface of the pigment (A) and in a non-aqueous solvent. A polymer (B) containing a polymerizable unsaturated group and at least one polymerizable unsaturated monomer (C) that is soluble in a non-aqueous solvent and becomes insoluble or hardly soluble after polymerization The pigment dispersion composition for color filters containing the modified pigment (D) which has the polymer (P) obtained by this is provided.
　また本発明は、色剤と樹脂と該樹脂を溶解し得る有機溶剤とから成るカラーフィルター用顔料分散組成物であって、色剤として、顔料(Ａ)、非水溶媒及び非水溶媒に可溶な重合性不飽和基を含有するポリマー（Ｂ）の存在下で、該非水溶媒に可溶でありかつ重合後に不溶もしくは難溶になる少なくとも１種の重合性不飽和単量体（Ｃ）を重合させる変性顔料（Ｄ）を含有するカラーフィルター用顔料分散組成物を提供する。 The present invention also relates to a pigment dispersion composition for a color filter comprising a colorant, a resin, and an organic solvent capable of dissolving the resin. The colorant may be a pigment (A), a nonaqueous solvent, or a nonaqueous solvent. At least one polymerizable unsaturated monomer (C) that is soluble in the non-aqueous solvent and insoluble or hardly soluble after polymerization in the presence of the polymer (B) containing a soluble polymerizable unsaturated group A pigment dispersion composition for a color filter, which contains a modified pigment (D) that polymerizes the above.
　本発明により、汎用の顔料を使用し、分散安定性に優れるカラーフィルター用顔料分散組成物を提供できる。 According to the present invention, a pigment dispersion composition for a color filter that uses a general-purpose pigment and is excellent in dispersion stability can be provided.
（変性顔料（Ｄ））
　本発明で着色剤として使用する変性顔料（Ｄ）は、汎用の顔料（Ａ）、非水溶媒、及び該非水溶媒に可溶な重合性不飽和基を含有するポリマー（Ｂ）の存在下で、該非水溶媒に可溶でありかつ重合後に不溶もしくは難溶になる少なくとも１種の重合性不飽和単量体（Ｂ）を重合させる、いわゆるｉｎ－ｓｉｔｕ重合により得ることができる。
　従来、ｉｎ－ｓｉｔｕ重合法は顔料が分散安定剤に微細かつ安定に分散された重合の場を必要とすると考えられていたが、本発明では非水溶媒に可溶な重合性不飽和基を含有するポリマー（Ｂ）で顔料（Ａ）の表面が濡らされる事により形成される顔料（Ａ）と非水溶媒に可溶な重合性不飽和基を含有するポリマー（Ｂ）の界面が重合の場になると考えられ、顔料が分散安定剤に微細かつ安定に分散された場は必須ではないため、微細に分散された状態を形成するための顔料の表面処理等は必ずしも必要ではなく、広範囲の種類の顔料に適用できるものである。 (Modified pigment (D))
The modified pigment (D) used as a colorant in the present invention is a general-purpose pigment (A), a non-aqueous solvent, and a polymer (B) containing a polymerizable unsaturated group soluble in the non-aqueous solvent. It can be obtained by so-called in-situ polymerization in which at least one polymerizable unsaturated monomer (B) that is soluble in the non-aqueous solvent and becomes insoluble or hardly soluble after polymerization is polymerized.
Conventionally, the in-situ polymerization method has been considered to require a polymerization field in which a pigment is finely and stably dispersed in a dispersion stabilizer. However, in the present invention, a polymerizable unsaturated group soluble in a non-aqueous solvent is added. The interface between the pigment (A) formed by wetting the surface of the pigment (A) with the polymer (B) contained and the polymer (B) containing a polymerizable unsaturated group soluble in a non-aqueous solvent is polymerized. It is not essential that the pigment is finely and stably dispersed in the dispersion stabilizer, and therefore surface treatment of the pigment to form a finely dispersed state is not always necessary, and a wide range of It can be applied to various types of pigments.
（顔料（Ａ））
　本発明で使用する顔料（Ａ）は、公知慣用の有機顔料あるいは無機顔料の中から選ばれる少なくとも一種の顔料である。また、本発明では未処理顔料、処理顔料のいずれでも適用することができる。 (Pigment (A))
The pigment (A) used in the present invention is at least one pigment selected from known and commonly used organic pigments or inorganic pigments. In the present invention, either an untreated pigment or a treated pigment can be applied.
　顔料（Ａ）としては、従来からカラーフィルターに使用されている市販の顔料、及び、「カラーインデックス便覧」（最新顔料便覧日本顔料技術協会編、１９７７年刊）「最新 顔料応用技術」（ＣＭＣ出版、１９８６年刊）「印刷インキ技術」（ＣＭＣ出版、１９８４年刊）等に記載されている公知慣用の顔料が挙げられる。
特にカラーフィルターで汎用的に使用される顔料として、具体的には、例えば、Ｃ．Ｉ．ピグメントレッド２５４やＣ．Ｉ．ピグメントレッド１７７やＣ．Ｉ．ピグメントオレンジ７１等のレッド顔料、Ｃ．Ｉ．ピグメントグリーン３６、Ｃ．Ｉ．ピグメントグリーン５８やＣ．Ｉ．ピグメントグリーン７等のグリーン顔料、Ｃ．Ｉ．ピグメントブルー１５：６やＣ．Ｉ．ピグメントブルー２２等のブルー顔料、Ｃ．Ｉ．ピグメントバイオレット２３やＣ．Ｉ．ピグメントバイオレット５０等のバイオレット顔料、Ｃ．Ｉ．ピグメントイエロー１３８、Ｃ．Ｉ．ピグメントイエロー１５０やＣ．Ｉ．ピグメントイエロー２０等のイエロー顔料、Ｃ．Ｉ．ピグメントブラック７、カーボンブラックやチタンブラック等の黒色顔料などが挙げられるが、これらの顔料は単独で用いることもでき、必要に応じて２種類以上を混合して用いることもできる。
一般に、カラーフィルター用顔料分散液の硬化塗膜の透明性は、含有する顔料の粒子径が小さいほど高くなるが、その一次粒子径は１０～８０ｎｍの範囲とすることが好ましく、３０～５０ｎｍの範囲とすることが特に好ましい。一次粒子径が１０ｎｍ未満では顔料の凝集性が高くなるので分散させ難くなってしまい、また、８０ｎｍを超えると透明性が低下する。 As the pigment (A), commercially available pigments conventionally used for color filters, and “Color Index Handbook” (edited by the Japan Pigment Technical Association, published in 1977) “Latest Pigment Applied Technology” (CMC Publishing, 1986) “Printing Ink Technology” (CMC Publishing Co., Ltd. published in 1984) and the like.
Specifically, as a pigment generally used in color filters, for example, C.I. I. Pigment red 254 and C.I. I. Pigment red 177 and C.I. I. Red pigments such as CI Pigment Orange 71; I. Pigment green 36, C.I. I. Pigment green 58 and C.I. I. Pigment Green 7 and other green pigments, C.I. I. Pigment blue 15: 6 and C.I. I. Blue pigments such as CI Pigment Blue 22; I. Pigment violet 23 and C.I. I. Violet pigments such as CI Pigment Violet 50, C.I. I. Pigment yellow 138, C.I. I. Pigment yellow 150 and C.I. I. Yellow pigments such as CI Pigment Yellow 20 and the like; I. Examples thereof include CI pigment black 7, black pigments such as carbon black and titanium black, and these pigments can be used alone or in combination of two or more as required.
In general, the transparency of a cured coating film of a pigment dispersion for a color filter increases as the particle diameter of the pigment contained decreases, but the primary particle diameter is preferably in the range of 10 to 80 nm, preferably 30 to 50 nm. The range is particularly preferable. If the primary particle diameter is less than 10 nm, the cohesiveness of the pigment becomes high, making it difficult to disperse, and if it exceeds 80 nm, the transparency is lowered.
（非水溶媒）
　本発明で使用する非水溶媒は、脂肪族および／または脂環式炭化水素系溶剤を必須とする有機溶剤である。脂肪族および／または脂環式炭化水素系溶剤としては、例えば、ｎ－ヘキサン、ｎ－ヘプタン、ｎ－オクタン、シェルケミカルズ社製品の「ロウス」もしくは「ミネラルスプリットＥＣ」、エクソンモービルケミカル社製品の「アイソパーＣ」、「アイソパーＥ」、「アイソパーＧ」、「アイソパーＨ」、「アイソパーＬ」、「アイソパーＭ」、「ナフサ３号」、「ナフサ５号」もしくは「ナフサ６号」、出光石油化学株式会社製品の「ソルベント７号」、「ＩＰソルベント１０１６」、「ＩＰソルベント１６２０」、「ＩＰソルベント２０２８」もしくは「ＩＰソルベント２８３５」、株式会社ジャパンエナジー製品の「ホワイトゾール」、丸善石油化学株式会社製品の「マルカゾール８」等が挙げられる。 (Non-aqueous solvent)
The non-aqueous solvent used in the present invention is an organic solvent in which an aliphatic and / or alicyclic hydrocarbon solvent is essential. Examples of the aliphatic and / or alicyclic hydrocarbon solvents include n-hexane, n-heptane, n-octane, “Loose” or “Mineral Split EC” of Shell Chemicals, and ExxonMobil Chemical. “Isopar C”, “Isopar E”, “Isopar G”, “Isopar H”, “Isopar L”, “Isopar M”, “Naphtha 3”, “Naphtha 5” or “Naphtha 6”, Idemitsu Oil “Solvent 7”, “IP Solvent 1016”, “IP Solvent 1620”, “IP Solvent 2028” or “IP Solvent 2835” of Chemical Co., Ltd., “Whitesol” of Japan Energy Products, Maruzen Petrochemical Co., Ltd. The company product “Marcazole 8” and the like can be mentioned.
　また、本発明の効果を損なわない範囲において、他の有機溶剤を混合して使用してもよい。このような有機溶剤としては、具体的には例えば、丸善石油化学株式会社製品の「スワゾール１００ないしは１５０」、トルエンもしくはキシレンの等の芳香族炭化水素系溶剤類；酢酸メチル、酢酸エチル、酢酸－ｎ－ブチルもしくは酢酸アミルの等のエステル類；アセトン、メチルエチルケトン、メチルイソブチルケトン、メチルアミルケトンもしくはシクロヘキサノンの等のケトン類；またはメタノール、エタノール、ｎ－プロパノール、ｉ－プロパノールもしくはｎ－ブタノールの等のアルコール類が挙げられる。
混合して使用する際には、前記脂肪族および／または脂環式炭化水素系溶剤の使用量を、５０質量％以上とすることが好ましく、より好ましくは６０質量％以上である。 Moreover, you may mix and use another organic solvent in the range which does not impair the effect of this invention. Specific examples of such organic solvents include “Swazole 100 or 150” manufactured by Maruzen Petrochemical Co., Ltd., aromatic hydrocarbon solvents such as toluene or xylene; methyl acetate, ethyl acetate, acetic acid- esters such as n-butyl or amyl acetate; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, methyl amyl ketone or cyclohexanone; or such as methanol, ethanol, n-propanol, i-propanol or n-butanol Examples include alcohols.
When mixed and used, the amount of the aliphatic and / or alicyclic hydrocarbon solvent used is preferably 50% by mass or more, and more preferably 60% by mass or more.
（非水溶媒に可溶な重合性不飽和基を含有するポリマー（Ｂ））
　本発明で使用する非水溶媒に可溶な重合性不飽和基を含有するポリマー（Ｂ）とは、具体的には、炭素原子数４個以上のアルキル基を有するアルキル（メタ）アクリレートを主成分とする重合性不飽和単量体の共重合体に重合性不飽和基を導入したポリマー、あるいは、炭素原子数４個以上のアルキル基を有するアルキル（メタ）アクリレートを主成分とする重合性不飽和単量体の共重合体からなるマクロモノマーなどを指称するものである。 (Polymer containing polymerizable unsaturated group soluble in non-aqueous solvent (B))
Specifically, the polymer (B) containing a polymerizable unsaturated group soluble in a nonaqueous solvent used in the present invention is mainly an alkyl (meth) acrylate having an alkyl group having 4 or more carbon atoms. Polymerization mainly comprising a polymer having a polymerizable unsaturated group introduced into a copolymer of a polymerizable unsaturated monomer as a component, or an alkyl (meth) acrylate having an alkyl group having 4 or more carbon atoms This term refers to a macromonomer composed of a copolymer of unsaturated monomers.
　炭素原子数４個以上のアルキル基を有するアルキル（メタ）アクリレートとしては、例えば、ｎ－ブチル（メタ）アクリレート、ｉ－ブチル（メタ）アクリレート、ｔ－ブチル（メタ）アクリレート、２－エチルヘキシル（メタ）アクリレート、ラウリル（メタ）アクリレート、ステアリル（メタ）アクリレート、イソステアリル（メタ）アクリレート、シクロヘキシル（メタ）アクリレート、等が挙げられる。
また、アルキル（メタ）アクリレート以外の使用が可能な重合性不飽和単量体として、スチレン、α－メチルスチレン、ｐ－ｔ－ブチルスチレンもしくはビニルトルエンの等の芳香族系ビニル系モノマー、ベンジル（メタ）アクリレート、ジメチルアミノ（メタ）アクリレート、ジエチルアミノ（メタ）アクリレート、ジブロモプロピル（メタ）アクリレートもしくはトリブロモフェニル（メタ）アクリレートの等の（メタ）アクリレート類、マレイン酸、フマル酸もしくはイタコン酸の等の不飽和ジカルボン酸と１価アルコールとのジエステル類、安息香酸ビニル、「ベオバ」（オランダ国シェル社製のビニルエステル）の等のビニルエステル類等が挙げられ、前記のアルキル（メタ）アクリレート類とともに共重合して使用することができる。
これらのアルキル（メタ）アクリレート以外の使用が可能な重合性不飽和基含有単量体の単独の重合体は該非水媒体での溶解性が低いため、アルキル（メタ）アクリレートとランダム重合体として使用されることが好ましい。ブロック状あるいはグラフト状に共重合を行った場合は、該非水媒体での溶解性を著しく低下させるため、あまり好ましくない。 Examples of the alkyl (meth) acrylate having an alkyl group having 4 or more carbon atoms include n-butyl (meth) acrylate, i-butyl (meth) acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meta ) Acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, isostearyl (meth) acrylate, cyclohexyl (meth) acrylate, and the like.
Polymerizable unsaturated monomers other than alkyl (meth) acrylates that can be used include aromatic vinyl monomers such as styrene, α-methylstyrene, pt-butylstyrene or vinyltoluene, benzyl ( (Meth) acrylate, dimethylamino (meth) acrylate, diethylamino (meth) acrylate, (meth) acrylates such as dibromopropyl (meth) acrylate or tribromophenyl (meth) acrylate, maleic acid, fumaric acid or itaconic acid, etc. And diesters of unsaturated dicarboxylic acids and monohydric alcohols, vinyl esters such as vinyl benzoate, “Veoba” (vinyl ester manufactured by Shell of the Netherlands), and the like, and the above alkyl (meth) acrylates Can be used together with copolymerization That.
A single polymer of a polymerizable unsaturated group-containing monomer that can be used other than these alkyl (meth) acrylates has low solubility in the non-aqueous medium, so it is used as an alkyl (meth) acrylate and a random polymer. It is preferred that When the copolymerization is carried out in the form of a block or a graft, the solubility in the non-aqueous medium is remarkably lowered, which is not preferable.
　これらの重合性不飽和単量体は単独で使用してもよいし、複数種を組み合わせて使用してもよい。中でも、ｎ－ブチル（メタ）アクリレート、２－エチルヘキシル（メタ）アクリレート、ラウリルメタクリレート等の炭素数４個から１２個のアルキル基を持つ直鎖あるいは分岐のアルキル（メタ）アクリレートの使用が特に好ましい。 These polymerizable unsaturated monomers may be used alone or in combination of two or more. Of these, the use of linear or branched alkyl (meth) acrylates having an alkyl group of 4 to 12 carbon atoms such as n-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl methacrylate and the like is particularly preferable.
　炭素原子数４個以上のアルキル基を有するアルキル（メタ）アクリレートを主成分とする重合性不飽和単量体の共重合体は、前記重合性不飽和単量体を常法により重合することで得られる。 A copolymer of a polymerizable unsaturated monomer having an alkyl (meth) acrylate having an alkyl group having 4 or more carbon atoms as a main component is obtained by polymerizing the polymerizable unsaturated monomer by a conventional method. can get.
　前記炭素原子数４個以上のアルキル基を有するアルキル（メタ）アクリレートを主成分とする重合性不飽和単量体の共重合体へ、重合性不飽和基を導入する事により、重合性不飽和基を含有するポリマー（Ｂ）が得られる。
重合性不飽和基の導入方法としては、例えば、予め前記共重合成分としてアクリル酸やメタクリル酸等のカルボキシル基含有重合性単量体や、ジメチルアミノエチルメタクリレートやジメチルアミノプロピルアクリルアミド等のアミノ基含有重合性単量体を配合し共重合させ、カルボキシル基やアミノ基を有する前記共重合体を得、次に該カルボキシル基やアミノ基と、グリシジルメタクリレート等のグリシジル基及び重合性不飽和基を有する単量体を反応させる方法、
予め前記共重合成分として２－ヒドロキシエチルメタクリレート、２－ヒドロキシエチルアクリレート等の水酸基含有単量体を配合し共重合させ、水酸基を有する前記共重合体を得、次に該水酸基と、イソシアネートエチルメタクリレートの等のイソシアネート基と重合性不飽和基を有する単量体を反応させる方法、
重合の際にチオグリコール酸を連鎖移動剤として使用して共重合体末端にカルボキシル基を導入し、該カルボキシル基に、グリシジルメタクリレートの等のグリシジル基と重合性不飽和基を有する単量体を反応させる方法、
重合開始剤として、アゾビスシアノペンタン酸の等のカルボキシル基含有アゾ開始剤を使用して共重合体にカルボキシル基を導入し、該カルボキシル基にグリシジルメタクリレートの等のグリシジル基と重合性不飽和基を有する単量体を反応させる方法等が挙げられる。中でも、アクリル酸やメタクリル酸等のカルボキシル基含有単量体あるいはジメチルアミノエチルメタクリレートやジメチルアミノプロピルアクリルアミド等のアミノ基含有単量体を共重合しておき、そのカルボキシル基あるいはアミノ基とグリシジルメタクリレートの等のグリシジル基と重合性不飽和基を有する単量体を反応させる方法が最も簡便であり好ましい。 By introducing a polymerizable unsaturated group into the copolymer of a polymerizable unsaturated monomer mainly comprising an alkyl (meth) acrylate having an alkyl group having 4 or more carbon atoms, polymerizable unsaturated A polymer (B) containing groups is obtained.
As a method for introducing a polymerizable unsaturated group, for example, a carboxyl group-containing polymerizable monomer such as acrylic acid or methacrylic acid or an amino group such as dimethylaminoethyl methacrylate or dimethylaminopropylacrylamide is previously used as the copolymer component. A polymerizable monomer is blended and copolymerized to obtain the copolymer having a carboxyl group or an amino group, and then having the carboxyl group or amino group, a glycidyl group such as glycidyl methacrylate, and a polymerizable unsaturated group. A method of reacting monomers,
A hydroxyl group-containing monomer such as 2-hydroxyethyl methacrylate or 2-hydroxyethyl acrylate is previously blended and copolymerized as the copolymer component to obtain the copolymer having a hydroxyl group, and then the hydroxyl group and isocyanate ethyl methacrylate are obtained. A method of reacting a monomer having a polymerizable unsaturated group with an isocyanate group such as
During polymerization, thioglycolic acid is used as a chain transfer agent to introduce a carboxyl group at the end of the copolymer, and a monomer having a glycidyl group such as glycidyl methacrylate and a polymerizable unsaturated group is added to the carboxyl group. How to react,
As a polymerization initiator, a carboxyl group-containing azo initiator such as azobiscyanopentanoic acid is used to introduce a carboxyl group into the copolymer, and a glycidyl group such as glycidyl methacrylate and a polymerizable unsaturated group are introduced into the carboxyl group. And the like. Among them, a carboxyl group-containing monomer such as acrylic acid or methacrylic acid or an amino group-containing monomer such as dimethylaminoethyl methacrylate or dimethylaminopropylacrylamide is copolymerized, and the carboxyl group or amino group and glycidyl methacrylate are copolymerized. A method of reacting a monomer having a polymerizable unsaturated group with a glycidyl group such as the simplest is preferable.
（非水溶媒に可溶でありかつ重合後に不溶もしくは難溶になる重合性不飽和単量体（Ｃ））
　本発明で使用する、該非水溶媒に可溶でありかつ重合後に不溶もしくは難溶になる重合性不飽和単量体（Ｃ）とは、具体的には例えば、メチル（メタ）アクリレート、エチル（メタ）アクリレート、ｎ－プロピル（メタ）アクリレートもしくはｉ－プロピル（メタ）アクリレート、または（メタ）アクリロニトリル、酢酸ビニル、塩化ビニル、塩化ビニリデン、フッ化ビニルもしくはフッ化ビニリデンのようなオレフィン類などの、いわゆる反応性極性基（官能基）をもたないビニル系モノマー類；（メタ）アクリルアミド、ジメチル（メタ）アクリルアミド、Ｎ－ｔ－ブチル（メタ）アクリルアミド、Ｎ－オクチル（メタ）アクリルアミド、ジアセトンアクリルアミド、ジメチルアミノプロピルアクリルアミドもしくはアルコキシ化Ｎ－メチロール化（メタ）アクリルアミド類などのアミド結合含有ビニル系モノマー類；ジアルキル〔（メタ）アクリロイロキシアルキル〕ホスフェート類もしくは（メタ）アクリロイロキシアルキルアシッドホスフェート類、またはジアルキル〔（メタ）アクリロイロキシアルキル〕ホスファイト類もしくは（メタ）アクリロイロキシアルキルアシッドホスファイト類；上記（メタ）アクリロイロキシアルキルアシッドホスフェート類ないしはアシッドホスファイト類のアルキレンオキシド付加物やグリシジル（メタ）アクリレートやメチルグリシジル（メタ）アクリレートなどエポキシ基含有ビニル系モノマーとリン酸または亜リン酸あるいはこれらの酸性エステル類とのエステル化合物をはじめ、３－クロロ－２－アシッドホスホキシプロピル（メタ）アクリレートなどのリン原子含有ビニル系モノマー類;２－ヒドロキシエチル（メタ）アクリレート、２－ヒドロキシプロピル（メタ）アクリレート、３－ヒドロキシプロピル（メタ）アクリレート、２－ヒドロキシブチル（メタ）アクリレート、３－ヒドロキシブチル（メタ）アクリレート、４－ヒドロキシブチル（メタ）アクリレート、３－クロロ－２－ヒドロキシプロピル（メタ）アクリレート、ジ－２－ヒドロキシエチルフマレートもしくはモノ－２－ヒドロキシエチルモノブチルフマレートまたは、ポリプロピレングリコールもしくは、ポリエチレングリコールモノ（メタ）アクリレート、あるいは「プラクセルＦＭ、ＦＡモノマー」（ダイセル化学株式会社製のカプロラクトン付加モノマー）の等の重合性不飽和カルボン酸のヒドロキシアルキルエステル類またはこれらとε－カプロラクトンとの付加物などをはじめ、（メタ）アクリル酸、クロトン酸、マレイン酸、フマル酸、イタコン酸もしくはシトラコン酸の等の不飽和モノ－ないしはジカルボン酸をはじめ、これらのジカルボン酸と１価のアルコールとのモノエステル類などの重合性不飽和カルボン酸類、または前記の重合性不飽和カルボン酸ヒドロキシアルキルエステル類とマレイン酸、コハク酸、フタル酸、ヘキサヒドロフタル酸、テトラヒドロフタル酸、ヘンゼントリカルボン酸、ベンゼンテトラカルボン酸、「ハイミック酸」、テトラクロルフタル酸もしくはドデシニルコハク酸の等のポリカルボン酸の無水物との付加物のような各種の不飽和カルボン酸類と「カージュラＥ」、やし油脂肪酸グリシジルエステルもしくはオクチル酸グリシジルエステルの等の１価のカルボン酸のモノグリシジルエステルまたはブチルグリシジルエーテル、エチレンオキシド、もしくはプロピレンオキシドの等のモノエポキシ化合物との付加物またはこれらとε－カプロラクトンとの付加物あるいはヒドロキシビニルエーテルのような水酸基含有重合性不飽和単量体類；ジメチルアミノエチル（メタ）アクリレート、ジエチルアミノエチル（メタ）アクリレートなどのジアルキルアミノアルキル（メタ）アクリレート類；グリシジル（メタ）アクリレート、（β－メチル）グルシジル（メタ）アクリレート、（メタ）アリルグルシジルエーテルもしくは重合性不飽和カルボン酸類またはモノ－２－（メタ）アクリロイルオキシモノエチルフタレートの等の水酸基含有ビニルモノマーと前記ポリカルボン酸無水物との等モル付加物の等の各種の不飽和カルボン酸に、「エピクロン２００」、「エピクロン４００」、「エピクロン４４１」、「エピクロン８５０」もしくは「エピクロン１０５０」（大日本インキ化学工業（株）製のエポキシ樹脂〕、または「エピコート８２８」、「エピコート１００１」もしくは「エピコート１００４」（ジャパンエポキシレジン株式会社製エポキシ樹脂）、「アラルダイト６０７１」もしくは「アラルダイト６０８４」（スイス国チバ・ガイギー社製のエポキシ樹脂）、さらには「チッソノックス２２１」〔チッソ株式会社製のエポキシ化合物〕、または「デナコールＥＸ－６１１」〔長瀬化成株式会社製のエポキシ化合物の等の、１分子中に少なくとも２個のエポキシ基を有する各種のポリエポキシ化合物を等モル比で付加反応させて得られるエポキシ基含有重合性化合物などのエポキシ基含有重合性不飽和単量体類；２－ヒドロキシエチル（メタ）アクリレート－ヘキサメチレンジイソシアネート等モル付加物や、イソシアネートエチル（メタ）アクリレートの等のイソシアネート基とビニル基とを有するモノマーなどのイソシアネート基含有α，β－エチレン性不飽和単量体類；ビニルエトキシシラン、α－メタクリロキシプロピルトリメトキシシラン、トリメチルシロキシエチル（メタ）アクリレート、「ＫＲ－２１５、Ｘ－２２－５００２」（信越化学工業株式会社製品）等のシリコン系モノマー類などのアルコキシシリル基含有重合性不飽和単量体類；そして、（メタ）アクリル酸、クロトン酸、マレイン酸、フマル酸、イタコン酸もしくはシトラコン酸の等の不飽和モノ－もしくはジカルボン酸をはじめ、これらのジカルボン酸と１価アルコールとのモノエステル類などのα，β－エチレン性不飽和カルボン酸類、または２－ヒドロキシエチル（メタ）アクリレート、２－ヒドロキシプロピル（メタ）アクリレート、３－ヒドロキシプロピル（メタ）アクリレート、２－ヒドロキシブチル（メタ）アクリレート、３－ヒドロキシブチル（メタ）アクリレート、４－ヒドロキシブチル（メタ）アクリレート、３－クロロ－２－ヒドロキシプロピル（メタ）アクリレート、ジ－２－ヒドロキシエチルフマレート、モノ－２－ヒドロキシエチル－モノブチルフマレートもしくはポリエチレングリコールモノ（メタ）アクリレートの等のα，β－不飽和カルボン酸ヒドロアルキルエステル類とマレイン酸、コハク酸、フタル酸、ヘキサヒドロフタル酸、テトラヒドロフタル酸、ベンゼントリカルボン酸、ベンゼンテトラカルボン酸、「ハイミック酸」、テトラクロルフタル酸もしくはドデシニルコハク酸の等のポリカルボン酸の無水物との付加物などのカルボキシル基含有α，β－エチレン性不飽和単量体類などがある。
　中でも、メチル（メタ）アクリレート、エチル（メタ）アクリレート等のＣ３以下のアルキル（メタ）アクリレート類の使用が好ましい。さらに、顔料表面の表面特性を変化させ、顔料分散剤あるいは顔料分散樹脂との相互作用を高めるために、少なくとも１種のカルボキシル基、スルホン酸基、リン酸基、ヒドロキシル基、ジメチルアミノ基等の官能基を含有する重合性不飽和単量体を、共重合する事が好ましい。 (Polymerizable unsaturated monomer (C) that is soluble in a non-aqueous solvent and becomes insoluble or hardly soluble after polymerization)
The polymerizable unsaturated monomer (C) used in the present invention that is soluble in the non-aqueous solvent and becomes insoluble or hardly soluble after polymerization is specifically exemplified by methyl (meth) acrylate, ethyl ( Such as olefins such as (meth) acrylate, n-propyl (meth) acrylate or i-propyl (meth) acrylate, or (meth) acrylonitrile, vinyl acetate, vinyl chloride, vinylidene chloride, vinyl fluoride or vinylidene fluoride, Vinyl monomers having no so-called reactive polar groups (functional groups); (meth) acrylamide, dimethyl (meth) acrylamide, Nt-butyl (meth) acrylamide, N-octyl (meth) acrylamide, diacetone acrylamide , Dimethylaminopropylacrylamide or alkoxylated N-methyl Amide bond-containing vinyl monomers such as rolled (meth) acrylamides; dialkyl [(meth) acryloyloxyalkyl] phosphates or (meth) acryloyloxyalkyl acid phosphates, or dialkyl [(meth) acryloyloxy Alkyl] phosphites or (meth) acryloyloxyalkyl acid phosphites; alkylene oxide adducts of the above (meth) acryloyloxyalkyl acid phosphates or acid phosphites, glycidyl (meth) acrylates and methylglycidyl (meta ) Ester compounds of epoxy group-containing vinyl monomers such as acrylates and phosphoric acid or phosphorous acid or their acidic esters, as well as 3-chloro-2-acid phosphoxypropyi Phosphorus atom-containing vinyl monomers such as (meth) acrylate; 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 3-chloro-2-hydroxypropyl (meth) acrylate, di-2-hydroxyethyl fumarate or mono-2-hydroxyethyl monobutyl fumarate Alternatively, polymerizable unsaturated carbo such as polypropylene glycol or polyethylene glycol mono (meth) acrylate, or “Placcel FM, FA monomer” (a caprolactone addition monomer manufactured by Daicel Chemical Industries, Ltd.) Hydroxyalkyl esters of acids or their adducts with ε-caprolactone, and unsaturated mono- or dicarboxylic acids such as (meth) acrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid or citraconic acid In addition, polymerizable unsaturated carboxylic acids such as monoesters of these dicarboxylic acids and monohydric alcohols, or the above-mentioned polymerizable unsaturated carboxylic acid hydroxyalkyl esters and maleic acid, succinic acid, phthalic acid, hexa Various unsaturations such as adducts with anhydrides of polycarboxylic acids such as hydrophthalic acid, tetrahydrophthalic acid, hensentricarboxylic acid, benzenetetracarboxylic acid, "hymic acid", tetrachlorophthalic acid or dodecynyl succinic acid Carboxylic acids and “Cardura E”, palm oil fatty acid group Monoglycidyl esters of monovalent carboxylic acids such as sidyl esters or glycidyl octyl esters or adducts with monoepoxy compounds such as butyl glycidyl ether, ethylene oxide or propylene oxide, or adducts thereof with ε-caprolactone or Hydroxyl-containing polymerizable unsaturated monomers such as hydroxy vinyl ether; Dialkylaminoalkyl (meth) acrylates such as dimethylaminoethyl (meth) acrylate and diethylaminoethyl (meth) acrylate; Glycidyl (meth) acrylate, (β- Methyl) glucidyl (meth) acrylate, (meth) allyl glycidyl ether or polymerizable unsaturated carboxylic acids or mono-2- (meth) acryloyloxymonoethyl phthalate, etc. Various unsaturated carboxylic acids such as an equimolar adduct of an acid group-containing vinyl monomer and the polycarboxylic acid anhydride are added to “Epicron 200”, “Epicron 400”, “Epicron 441”, “Epicron 850” or “Epicron”. "Epicron 1050" (epoxy resin manufactured by Dainippon Ink & Chemicals, Inc.), "Epicoat 828", "Epicoat 1001" or "Epicoat 1004" (Epoxy resin manufactured by Japan Epoxy Resin Co., Ltd.), "Araldite 6071" or " Araldite 6084 "(an epoxy resin manufactured by Ciba-Geigy, Switzerland), and further," Chissonox 221 "[an epoxy compound manufactured by Chisso Corporation], or" Denacol EX-611 "[an epoxy compound manufactured by Nagase Kasei Co., Ltd.] At least two per molecule Epoxy group-containing polymerizable unsaturated monomers such as epoxy group-containing polymerizable compounds obtained by addition reaction of various polyepoxy compounds having a poxy group at an equimolar ratio; 2-hydroxyethyl (meth) acrylate-hexa Isocyanate group-containing α, β-ethylenically unsaturated monomers such as methylene diisocyanate equimolar adducts and monomers having an isocyanate group and a vinyl group such as isocyanate ethyl (meth) acrylate; vinyl ethoxysilane, α- Alkoxysilyl group-containing polymerizable unsaturation such as methacryloxypropyltrimethoxysilane, trimethylsiloxyethyl (meth) acrylate, silicon monomers such as “KR-215, X-22-5002” (product of Shin-Etsu Chemical Co., Ltd.) Monomers; and (meth) acrylic acid, croton Α, β-ethylenically unsaturated carboxylic acids such as unsaturated mono- or dicarboxylic acids such as acid, maleic acid, fumaric acid, itaconic acid or citraconic acid, and monoesters of these dicarboxylic acids with monohydric alcohols Acids, or 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, 4- Hydroxybutyl (meth) acrylate, 3-chloro-2-hydroxypropyl (meth) acrylate, di-2-hydroxyethyl fumarate, mono-2-hydroxyethyl monobutyl fumarate or polyethylene glycol mono (meth) acrylate, etc. Α, -Unsaturated carboxylic acid hydroalkyl esters of maleic acid, succinic acid, phthalic acid, hexahydrophthalic acid, tetrahydrophthalic acid, benzenetricarboxylic acid, benzenetetracarboxylic acid, "hymic acid", tetrachlorophthalic acid or dodecynyl succinic acid Carboxyl group-containing α, β-ethylenically unsaturated monomers such as adducts of polycarboxylic acid anhydrides and the like.
Of these, the use of C3 or lower alkyl (meth) acrylates such as methyl (meth) acrylate and ethyl (meth) acrylate is preferred. Furthermore, in order to change the surface characteristics of the pigment surface and enhance the interaction with the pigment dispersant or pigment dispersion resin, at least one kind of carboxyl group, sulfonic acid group, phosphoric acid group, hydroxyl group, dimethylamino group, etc. It is preferable to copolymerize a polymerizable unsaturated monomer containing a functional group.
　また、変性顔料（Ｄ）の使用時に顔料（Ａ）からポリマーを溶出させないために、該ポリマーは架橋していると尚好ましい。架橋成分として使用する多官能重合性不飽和単量体としては、例えば、ジビニルベンゼン、エチレングリコールジ（メタ）アクリレート、ジエチレングリコールジ（メタ）アクリレート、トリエチレングリコールジ（メタ）アクリレート、ポリエチレングリコールジ（メタ）アクリレート、１，３－ブタンジオールジ（メタ）アクリレート、１，４－ブタンジオールジ（メタ）アクリレート、１，６－ヘキサンジオールジ（メタ）アクリレート、ネオペンチルグリコールジメタクリレート、トリメチロールプロパントリエトキシトリ（メタ）アクリレート、トリメチロールプロパントリ（メタ）アクリレート、ペンタエリスリトールトリ（メタ）アクリレート、ペンタエリスリトールテトラ（メタ）アクリレート、ジペンタエリスリトールヘキサ（メタ）アクリレート、またはアリルメタクリレート等が挙げられる。 In order to prevent the polymer from eluting from the pigment (A) when the modified pigment (D) is used, it is more preferable that the polymer is crosslinked. Examples of the polyfunctional polymerizable unsaturated monomer used as the crosslinking component include divinylbenzene, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, polyethylene glycol di ( (Meth) acrylate, 1,3-butanediol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol dimethacrylate, trimethylolpropane tri Ethoxytri (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol Sa (meth) acrylate or allyl methacrylate, and the like.
　また、少なくとも１種の該非水溶媒に可溶でありかつ重合後に不溶もしくは難溶になる重合性不飽和単量体（Ｃ）を必須成分とするポリマーが該非水溶媒系で溶解しない使用範囲において、その他の重合性不飽和単量体を使用してもよい。その他の重合性不飽和単量体としては、例えば前述の炭素原子数４個以上のアルキル基を有するアルキル（メタ）アクリレートや前記のアルキル（メタ）アクリレート以外の使用が可能な重合性不飽和単量体が挙げられる。 Further, in a use range in which a polymer having an essential component of a polymerizable unsaturated monomer (C) which is soluble in at least one non-aqueous solvent and becomes insoluble or hardly soluble after polymerization is not dissolved in the non-aqueous solvent system. Other polymerizable unsaturated monomers may be used. Examples of other polymerizable unsaturated monomers include polymerizable unsaturated monomers that can be used other than the alkyl (meth) acrylate having an alkyl group having 4 or more carbon atoms and the alkyl (meth) acrylate described above. A monomer is mentioned.
　本発明で使用する変性顔料（Ｄ）は、顔料（Ａ）、非水溶媒、及び該非水溶媒に可溶な重合性不飽和基を含有するポリマー（Ｂ）の存在下で、該非水溶媒に可溶でありかつ重合後に不溶もしくは難溶になる少なくとも１種の重合性不飽和単量体（Ｃ）を重合させることで得られる。
　顔料（Ａ）と非水溶媒に可溶な重合性不飽和基を含有するポリマー（Ｂ）は、重合を行う前に混合することが好ましい。混合方法としては、例えば、ホモジナイザー、ディスパー、ビーズミル、ペイントシェーカー、ニーダー、ロールミル、ボールミル、アトライター、サンドミル等を使用することが可能である。本発明においては、使用する顔料の形態は問わず、スラリー、ウエットケーキ、粉体のいずれの形態でもかまわない。即ち、本発明の製造方法においては、ウエットケーキのような水を含む顔料であっても使用可能である。
　前記顔料（Ａ）と前記ポリマー（Ｂ）の混合後に、重合性不飽和単量体（Ｃ）および後述の重合開始剤をさらに混合し、重合を行う事で変性顔料（Ｄ）が得られる。
　その際、前記ポリマー（Ｂ）の使用量は目的に応じて適宜最適化されるので特に限定はないが、通常は顔料（Ａ）１００部に対して１～２００部を使用し、より好ましくは５～５０部、さらに好ましくは５～３０部である。
　また、前記重合性不飽和単量体（Ｃ）の使用量も、目的に応じて適宜最適化されるので特に限定はないが、通常は顔料（Ａ）１００部に対して１～２００部を使用し、より好ましくは５～５０部、さらに好ましくは５～３０部である。 The modified pigment (D) used in the present invention contains a pigment (A), a non-aqueous solvent, and a polymer (B) containing a polymerizable unsaturated group soluble in the non-aqueous solvent. It is obtained by polymerizing at least one polymerizable unsaturated monomer (C) that is soluble and insoluble or hardly soluble after polymerization.
The pigment (A) and the polymer (B) containing a polymerizable unsaturated group soluble in a non-aqueous solvent are preferably mixed before polymerization. As a mixing method, for example, a homogenizer, a disper, a bead mill, a paint shaker, a kneader, a roll mill, a ball mill, an attritor, a sand mill and the like can be used. In the present invention, the form of the pigment to be used is not limited, and any form of slurry, wet cake, and powder may be used. That is, in the production method of the present invention, even a pigment containing water such as a wet cake can be used.
After mixing the pigment (A) and the polymer (B), the polymerizable unsaturated monomer (C) and a polymerization initiator described later are further mixed and polymerized to obtain the modified pigment (D).
At that time, the amount of the polymer (B) used is not particularly limited because it is appropriately optimized depending on the purpose, but usually 1 to 200 parts are used, more preferably 100 parts of the pigment (A). 5 to 50 parts, more preferably 5 to 30 parts.
The amount of the polymerizable unsaturated monomer (C) used is also not particularly limited since it is appropriately optimized depending on the purpose, but usually 1 to 200 parts per 100 parts of the pigment (A). More preferably 5 to 50 parts, still more preferably 5 to 30 parts.
　最終的に顔料にコートされる前記ポリマー（Ｐ）の量は、顔料（Ａ）１００部に対して、２～４００部が好ましく使用され、より好ましくは１０～１００部、さらに好ましくは１０～６０部である。その際、前記ポリマー（Ｂ）の１００部に対して、少なくとも１種の前記重合性不飽和単量体（Ｃ）は通常１０～４００部の割合で使用することが好ましく、好ましくは３０～４００部、さらに好ましくは５０～２００部である。 The amount of the polymer (P) finally coated on the pigment is preferably 2 to 400 parts, more preferably 10 to 100 parts, still more preferably 10 to 60 parts per 100 parts of the pigment (A). Part. At that time, it is preferable to use at least one polymerizable unsaturated monomer (C) in a proportion of usually 10 to 400 parts, preferably 30 to 400 parts, per 100 parts of the polymer (B). Parts, more preferably 50 to 200 parts.
　前記顔料（Ａ）、前記非水溶媒、及び前記ポリマー（Ｂ）の存在下で、前記重合性不飽和単量体（Ｃ）を重合させる方法は、公知慣用の重合方法によって行えばよいが、通常は重合開始剤の存在下で行う。かかる重合開始剤としては、アゾビスイソブチロニトリル（ＡＩＢＮ）、２，２－アゾビス（２－メチルブチロニトリル）、ベンゾイルパーオキシド、ｔ－ブチルパーベンゾエート、ｔ－ブチル－２－エチルヘキサノエート、ｔ－ブチルハイドロパーオキシド、ジ－ｔ－ブチルパーオキシド、またはクメンハイドロパーオキシドなどのラジカル発生重合触媒が単独で、あるいは２種以上の併用の形で用いられる。
　重合開始剤は該非水溶媒系に溶解し難いものもあるため、前記重合性不飽和単量体（Ｃ）に溶解し、顔料（Ａ）と前記ポリマー（Ｂ）の混合系に加える方法が好ましい。
　また、前記重合性不飽和単量体（Ｃ）あるいは重合開始剤を溶解した前記重合性不飽和単量体（Ｃ）は、重合温度に達した状態で滴下法により加えることもできるが、昇温前の常温の状態で加え、充分に混合された後に昇温し、重合させる方法が安定であり好ましい。
　重合温度は通常６０℃～１３０℃の範囲である。また顔料（Ａ）が有機顔料の場合、重合温度があまり高温では該顔料の変質や結晶成長などの形態変化が著しい場合があるため、その場合は７０～１００℃で重合することが好ましい。 A method of polymerizing the polymerizable unsaturated monomer (C) in the presence of the pigment (A), the non-aqueous solvent, and the polymer (B) may be performed by a known and conventional polymerization method. Usually, it is carried out in the presence of a polymerization initiator. Such polymerization initiators include azobisisobutyronitrile (AIBN), 2,2-azobis (2-methylbutyronitrile), benzoyl peroxide, t-butyl perbenzoate, t-butyl-2-ethylhexano A radical generating polymerization catalyst such as ate, t-butyl hydroperoxide, di-t-butyl peroxide, or cumene hydroperoxide is used alone or in combination of two or more.
Since some polymerization initiators are difficult to dissolve in the non-aqueous solvent system, a method in which the polymerization initiator is dissolved in the polymerizable unsaturated monomer (C) and added to the mixed system of the pigment (A) and the polymer (B) is preferable. .
The polymerizable unsaturated monomer (C) or the polymerizable unsaturated monomer (C) in which the polymerization initiator is dissolved can be added by a dropping method in a state where the polymerization temperature is reached. A method of adding the polymer at a normal temperature before warming, heating the polymer after sufficiently mixing, and polymerizing is stable and preferable.
The polymerization temperature is usually in the range of 60 ° C to 130 ° C. In the case where the pigment (A) is an organic pigment, if the polymerization temperature is too high, the pigment may undergo significant changes in shape such as alteration or crystal growth. In such a case, it is preferable to polymerize at 70 to 100 ° C.
　重合後、ろ過により重合に使用した非水溶媒等を除去し、さらに乾燥、粉砕を行う事で粉体のポリマーコート顔料として得ることができる。ろ過方法には、ヌッチェ、フィルタープレス等を使用できる。また乾燥には、箱型乾燥機、真空乾燥機、バンド乾燥機、スプレードライヤー等の公知の乾燥装置により乾燥することができる。また粉砕には、乳鉢、ハンマーミル、ディスクミル、ピンミル、ジェットミル等の公知の粉砕装置を使用することができる。 After polymerization, the non-aqueous solvent used for the polymerization is removed by filtration, followed by drying and pulverization to obtain a powdery polymer-coated pigment. Nutsche, filter press, etc. can be used for the filtration method. Moreover, it can dry with well-known drying apparatuses, such as a box-type dryer, a vacuum dryer, a band dryer, and a spray dryer. For the pulverization, a known pulverizer such as a mortar, a hammer mill, a disk mill, a pin mill, or a jet mill can be used.
（カラーフィルター用顔料分散組成物）
　本発明のカラーフィルター用顔料分散組成物は、変性顔料（Ｄ）を、樹脂等の顔料分散剤および有機溶剤を混合した樹脂溶液中に分散する事により得られる。その際、公知慣用の顔料分散方法を使用する事ができ、ボールミル、サンドミル、ビーズミル、３本ロールミル、ペイントコンディショナー、アトライター、分散攪拌機、超音波等の分散機を使用して、顔料分散を行う事ができる。具体的な分散機器としては、スーパーアペックスミル（コトブキ技研工業社製）、ウルトラアペックスミル（コトブキ技研工業社製）、ドライスヴェルケＰＭ―ＤＣＰ撹拌式ビーズミル装置（ドライスヴェルケ社製）、ピコグレンミル（浅田鉄工（株）製）等を挙げることができる。 (Pigment dispersion composition for color filter)
The pigment dispersion composition for a color filter of the present invention can be obtained by dispersing the modified pigment (D) in a resin solution in which a pigment dispersant such as a resin and an organic solvent are mixed. At that time, a publicly known and commonly used pigment dispersion method can be used, and the pigment dispersion is performed using a dispersing machine such as a ball mill, a sand mill, a bead mill, a three-roll mill, a paint conditioner, an attritor, a dispersion stirrer, or an ultrasonic wave. I can do things. Specific dispersing equipment includes super apex mill (manufactured by Kotobuki Giken Kogyo Co., Ltd.), ultra apex mill (manufactured by Kotobuki Giken Kogyo Co., Ltd.), dry swerke PM-DCP stirring bead mill device (manufactured by dry swerke), pico glen mill ( Asada Iron Works Co., Ltd.).
　顔料分散の際に用いる摩砕媒介物としては、例えば、ジルコニア製又は鋼製の摩砕媒介物が挙げられ、これらの中でも、耐摩耗性に優れるジルコニア製の摩砕媒介物が特に好ましい。また、摩砕媒介物の直径は、０．０１～３．０ｍｍの範囲が好ましく、０．０５～０．５ｍｍの範囲が特に好ましい。摩砕媒介物の直径が３．０ｍｍよりも大きい場合、湿式微粉砕が不十分となり、好ましくない。 Examples of the grinding medium used for pigment dispersion include a zirconia or steel grinding medium, and among these, a zirconia grinding medium having excellent wear resistance is particularly preferable. The diameter of the grinding mediator is preferably in the range of 0.01 to 3.0 mm, particularly preferably in the range of 0.05 to 0.5 mm. When the diameter of the grinding medium is larger than 3.0 mm, the wet pulverization becomes insufficient, which is not preferable.
　顔料分散の際に用いる顔料分散剤としては、一般に顔料分散に使用されている公知の顔料分散剤を使用することができる。例を挙げれば、界面活性剤、顔料の中間体もしくは誘導体、染料の中間体もしくは誘導体、あるいは、ポリアミド系樹脂、ポリウレタン系樹脂、ポリエステル系樹脂、アクリル系樹脂などの樹脂型分散剤が挙げられる。上記各種分散剤の中でも、ポリエステル系およびアクリル系樹脂を使用するのが好ましい。
　樹脂型分散剤の市販品としては、例えば、ビックケミー社製品の「ＤＩＳＰＥＲＢＹＫ－１３０」、「ＤＩＳＰＥＲＢＹＫ－１６１」、「ＤＩＳＰＥＲＢＹＫ－１６２」、「ＤＩＳＰＥＲＢＹＫ－１６３」、「ＤＩＳＰＥＲＢＹＫ－１７０」、「ＤＩＳＰＥＲＢＹＫ－１７１」、「ＤＩＳＰＥＲＢＹＫ－１７４」、「ＤＩＳＰＥＲＢＹＫ－１８０」、「ＤＩＳＰＥＲＢＹＫ－１８２」、「ＤＩＳＰＥＲＢＹＫ－１８３」、「ＤＩＳＰＥＲＢＹＫ－１８４」、「ＤＩＳＰＥＲＢＹＫ－１８５」、「ＤＩＳＰＥＲＢＹＫ－２０００」、「ＤＩＳＰＥＲＢＹＫ－２００１」、「ＤＩＳＰＥＲＢＹＫ－２０２０」、「ＤＩＳＰＥＲＢＹＫ－２０５０」、「ＤＩＳＰＥＲＢＹＫ－２０７０」、「ＤＩＳＰＥＲＢＹＫ－２０９６」、「ＤＩＳＰＥＲＢＹＫ－２１５０」、チバスペシャルティーケミカルズ社製品の「ＥＦＫＡ１５０３」、「ＥＦＫＡ４０１０」、「ＥＦＫＡ４０２０」、「ＥＦＫＡ４３００」、「ＥＦＫＡ４３３０」、「ＥＦＫＡ４３４０」、「ＥＦＫＡ４５２０」、「ＥＦＫＡ４５３０」、「ＥＦＫＡ５０５４」、「ＥＦＫＡ７４１１」、「ＥＦＫＡ７４２２」、「ＥＦＫＡ７４３１」、「ＥＦＫＡ７４４１」、「ＥＦＫＡ７４６１」、「ＥＦＫＡ７４９６」、「ＥＦＫＡ７４９７」、ルーブリゾール社製品の「ソルスパース３０００」、「ソルスパース９０００」、「ソルスパース１３２４０」、「ソルスパース１３６５０」、「ソルスパース１３９４０」、「ソルスパース１７０００」、「ソルスパース１８０００」、「ソルスパース２００００」、「ソルスパース２１０００」、「ソルスパース２００００」、「ソルスパース２４０００」、「ソルスパース２６０００」、「ソルスパース２７０００」、「ソルスパース２８０００」、「ソルスパース３２０００」、「ソルスパース３６０００」、「ソルスパース３７０００」、「ソルスパース３８０００」、「ソルスパース４１０００」、「ソルスパース４２０００」、「ソルスパース４３０００」、「ソルスパース４６０００」、「ソルスパース５４０００」、「ソルスパース７１０００」、味の素ファインテクノ株式会社製品のアジスパー「ＰＢ－７１１」、「アジスパーＰＢ－８２１」、「アジスパーＰＢ－８２２」、「アジスパーＰＢ－８１４」、「アジスパーＰＢ－８２４」などを用いることが可能である。
　また、レベリング剤、カップリング剤、カチオン系の界面活性剤なども併せて使用可能である。本発明において、これらの分散剤は、２種以上を併用することもできる。 As the pigment dispersant used in the pigment dispersion, a known pigment dispersant generally used for pigment dispersion can be used. Examples include surfactants, pigment intermediates or derivatives, dye intermediates or derivatives, or resin-type dispersants such as polyamide resins, polyurethane resins, polyester resins, and acrylic resins. Among the above various dispersants, it is preferable to use a polyester-based resin and an acrylic resin.
Commercially available resin-type dispersants include, for example, “DISPERBYK-130”, “DISPERBYK-161”, “DISPERBYK-162”, “DISPERBYK-163”, “DISPERBYK-170”, “DISPERBYK-171” manufactured by BYK Chemie. ”,“ DISPERBYK-174 ”,“ DISPERBYK-180 ”,“ DISPERBYK-182 ”,“ DISPERBYK-183 ”,“ DISPERBYK-184 ”,“ DISPERBYK-185 ”,“ DISPERBYK-2000 ”,“ DISPERBYK-2001 ”, “DISPERBYK-2020”, “DISPERBYK-2050”, “DISPERBYK-2070”, “DISPERBYK-2096”, “DISPERBYK” 2150 ”,“ EFKA1503 ”,“ EFKA4010 ”,“ EFKA4020 ”,“ EFKA4300 ”,“ EFKA4330 ”,“ EFKA4340 ”,“ EFKA4520 ”,“ EFKA4530 ”,“ EFKA5054 ”,“ EFK5054 ”,“ EFT50505 ” "EFKA7422", "EFKA7431", "EFKA7441", "EFKA7461", "EFKA7496", "EFKA7496", Lubrizol's "Solsparse 3000", "Solsparse 9000", "Solsparse 13240", "Solsparse 13650", ""Sol Sparse 13940", "Sol Sparse 17000", "Sol Sparse 18000", "Sol Sparse 20000", "Sol Sparse 210" 0, “Sol Sparse 20000”, “Sol Sparse 24000”, “Sol Sparse 26000”, “Sol Sparse 27000”, “Sol Sparse 28000”, “Sol Sparse 32000”, “Sol Sparse 36000”, “Sol Sparse 37000”, “Sol Sparse 38000”, “Sol Sparse” "41000", "Solspers 42000", "Solspers 43000", "Solspers 46000", "Solspers 54000", "Solspers 71000", Ajinomoto Fine Techno Co., Ltd. products Ajispar "PB-711", "Aispers PB-821", " It is possible to use “Azisper PB-822”, “Azisper PB-814”, “Azisper PB-824”, and the like.
In addition, a leveling agent, a coupling agent, a cationic surfactant, and the like can be used together. In the present invention, these dispersants may be used in combination of two or more.
　顔料分散の際に使用する有機溶剤としては、例えば、トルエンやキシレン、メトキシベンゼン等の芳香族系溶剤、酢酸エチル、酢酸プロピルや酢酸ブチル、プロピレングリコールモノメチルエーテルアセテート、プロピレングリコールモノエチルエーテルアセテート等の酢酸エステル系溶剤、エトキシエチルプロピオネート等のプロピオネート系溶剤、メタノール、エタノール等のアルコール系溶剤、ブチルセロソルブ、プロピレングリコールモノメチルエーテル、ジエチレングリコールエチルエーテル、ジエチレングリコールジメチルエーテル等のエーテル系溶剤、メチルエチルケトン、メチルイソブチルケトン、シクロヘキサノン等のケトン系溶剤、ヘキサン等の脂肪族炭化水素系溶剤、Ｎ，Ｎ－ジメチルホルムアミド、γ－ブチロラクタム、Ｎ－メチル－２－ピロリドン、アニリン、ピリジン等の窒素化合物系溶剤、γ－ブチロラクトン等のラクトン系溶剤、カルバミン酸メチルとカルバミン酸エチルの４８：５２の混合物の様なカルバミン酸エステル、水等が挙げられる。中でも、特にプロピオネート、アルコール系、エーテル系、ケトン系、窒素化合物系、ラクトン系等の極性溶媒で水可溶のものが好ましい。水可溶の有機溶剤を使用する場合には、それに水を併用することもできる。本発明において、これらの溶剤は、２種以上を併用することもできる。 Examples of the organic solvent used for pigment dispersion include aromatic solvents such as toluene, xylene and methoxybenzene, ethyl acetate, propyl acetate and butyl acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate and the like. Acetic acid ester solvents, propionate solvents such as ethoxyethyl propionate, alcohol solvents such as methanol and ethanol, ether solvents such as butyl cellosolve, propylene glycol monomethyl ether, diethylene glycol ethyl ether, diethylene glycol dimethyl ether, methyl ethyl ketone, methyl isobutyl ketone, Ketone solvents such as cyclohexanone, aliphatic hydrocarbon solvents such as hexane, N, N-dimethylformamide, γ-butyrolas Nitride-based solvents such as Tam, N-methyl-2-pyrrolidone, aniline and pyridine, lactone-based solvents such as γ-butyrolactone, carbamate esters such as a 48:52 mixture of methyl carbamate and ethyl carbamate, water Etc. Of these, water-soluble polar solvents such as propionate, alcohol, ether, ketone, nitrogen compound, and lactone are particularly preferable. When a water-soluble organic solvent is used, water can be used in combination. In this invention, these solvents can also use 2 or more types together.
　それぞれの使用比率については特に限定はないが、一般的に、変性顔料（Ｄ）の１００部に対して、５～２００部の顔料分散剤、好ましくは、１０～１００の顔料分散剤、さらに好ましくは、１０～６０の顔料分散剤を用い、有機溶剤は、変性顔料（Ｄ）と顔料分散剤の固形分量の合計が１０～２５％、好ましくは１０～２０％になる様に使用される。 Although there is no particular limitation on the use ratio of each, generally 5 to 200 parts of pigment dispersant, preferably 10 to 100 pigment dispersant, more preferably 100 parts of the modified pigment (D). 10 to 60 pigment dispersant is used, and the organic solvent is used so that the total solid content of the modified pigment (D) and the pigment dispersant is 10 to 25%, preferably 10 to 20%.
（カラーフィルター）
　本発明のカラーフィルター用顔料分散組成物は、赤色、緑色、青色の各色画素部およびブラックマトリックスを有するカラーフィルターの製造に用いることが出来る。
　カラーフィルターを製造するに当たっては、フォトリソグラフィー法、インクジェット法、印刷法等の公知慣用の製造方法がいずれも採用できる。以下フォトリソグラフィー法の例に説明する。
　フォトリソグラフィー法は、本発明のカラーフィルター用顔料分散組成物に光硬化性のモノマーやオリゴマー、光重合開始剤等を適宜混合した光硬化性組成物を、カラーフィルター用の透明基板のブラックマトリックスを設けた側の面に塗布、加熱乾燥（プリベーク）した後、フォトマスクを介して２００～５００ｎｍの波長範囲の紫外線あるいは可視光を照射することでパターン露光を行って、画素部に対応する箇所の光硬化性化合物を硬化させ、次いで未露光部分を現像液で現像し、非画素部を除去して画素部を透明基板に固着させる方法である。この方法では、光硬化性組成物の硬化着色皮膜からなる画素部が透明基板上に形成される。黒色、赤色、緑色および青色の変性顔料（Ｄ）毎に光硬化性組成物を調製して、前記した操作を繰り返すことにより、ブラックマトリックスを形成し、さらに所定の位置に赤色、緑色、青色の各色画素部を有するカラーフィルターを製造することができる。
　また、赤色、緑色および青色等の画素部の形成には、黄色の変性顔料（Ｄ）や紫色の変性顔料（Ｄ）を併用することも出来る。また必要に応じて光硬化後カラーフィルター全体を加熱処理（ポストベーク）することもできる。 (Color filter)
The pigment dispersion composition for a color filter of the present invention can be used for producing a color filter having red, green and blue color pixel portions and a black matrix.
In producing the color filter, any known and commonly used production methods such as a photolithography method, an ink jet method, and a printing method can be employed. Hereinafter, an example of a photolithography method will be described.
The photolithographic method uses a photocurable composition in which a photocurable monomer or oligomer, a photopolymerization initiator, or the like is appropriately mixed with the pigment dispersion composition for a color filter of the present invention, and a black matrix of a transparent substrate for a color filter. After applying and heating and drying (pre-baking) the surface on the provided side, pattern exposure is performed by irradiating ultraviolet rays or visible light in the wavelength range of 200 to 500 nm through a photomask, and the portions corresponding to the pixel portions are exposed. In this method, the photocurable compound is cured, and then the unexposed portion is developed with a developer, the non-pixel portion is removed, and the pixel portion is fixed to the transparent substrate. In this method, a pixel portion made of a cured colored film of a photocurable composition is formed on a transparent substrate. A photocurable composition is prepared for each of the black, red, green, and blue modified pigments (D), and the above-described operation is repeated to form a black matrix. Further, red, green, and blue are formed at predetermined positions. A color filter having each color pixel portion can be manufactured.
In addition, yellow modified pigment (D) or purple modified pigment (D) can be used in combination for the formation of red, green and blue pixel portions. If necessary, the entire color filter after photocuring can be heat-treated (post-baked).
　前記光硬化性組成物をガラス等の透明基板上に塗布する方法としては、例えば、スピンコート法、ロールコート法、インクジェット法等が挙げられる。また塗布後の光硬化性組成物の加熱乾燥条件は、各成分の種類、配合割合等によっても異なるが、通常、５０～１５０℃で、１～１５分間程度である。
　また、パターン露光後の現像方法としては、例えば、液盛り法、ディッピング法、スプレー法等が挙げられる。光硬化性組成物の露光、現像の後に、必要な色の画素部が形成された透明基板は水洗し乾燥させる。
　こうして得られたカラーフィルターは、ホットプレート、オーブン等の加熱装置により、１００～２８０℃で、所定時間加熱処理（ポストベーク）することによって、塗膜中の揮発性成分を除去すると同時に、光硬化性組成物の硬化着色皮膜中に残存する未反応の光硬化性化合物が熱硬化し、カラーフィルターが完成する。 Examples of the method for applying the photocurable composition onto a transparent substrate such as glass include a spin coating method, a roll coating method, and an inkjet method. The heat drying conditions of the photocurable composition after coating vary depending on the type of each component, the blending ratio, etc., but is usually 50 to 150 ° C. for about 1 to 15 minutes.
Examples of the developing method after pattern exposure include a liquid piling method, a dipping method, and a spray method. After exposure and development of the photocurable composition, the transparent substrate on which the necessary color pixel portions are formed is washed with water and dried.
The color filter thus obtained is subjected to a heat treatment (post-baking) at 100 to 280 ° C. for a predetermined time by a heating device such as a hot plate or an oven to remove volatile components in the coating film and at the same time photo-curing. The unreacted photocurable compound remaining in the cured colored film of the curable composition is thermally cured to complete the color filter.
　顔料分散法のうちフォトリソグラフィー法によるカラーフィルターの製造方法について詳述したが、本発明のカラーフィルター用顔料分散組成物を用いたカラーフィルターは該方法に限定されることなく、例えば電着法、転写法、ミセル電解法、ＰＶＥＤ（Ｐｈｏｔｏｖｏｌｔａｉｃ　Ｅｌｅｃｔｒｏｄｅｐｏｓｉｔｉｏｎ）法等の方法で製造してもよい。 The method for producing a color filter by a photolithography method among the pigment dispersion methods has been described in detail, but the color filter using the pigment dispersion composition for a color filter of the present invention is not limited to the method, for example, an electrodeposition method, You may manufacture by methods, such as a transcription | transfer method, a micelle electrolysis method, and PVED (Photovoltaic Electrodeposition) method.
　以下、本発明を実施例により説明する。特に断りのない限り、「部」および「％」は質量基準である。 Hereinafter, the present invention will be described by way of examples. Unless otherwise specified, “parts” and “%” are based on mass.
＜参考例１　非水溶媒に可溶な重合性不飽和基を含有するポリマー（Ｂ－１）の合成＞
　温度計、攪拌機、還流冷却器および窒素ガス導入管を備えた四つ口フラスコに、ヘプタンの５００部、酢酸ブチルの４７０部を仕込んで９０℃に昇温し、同温度に達したところで、アクリル酸ブチルの９８５部、メタクリル酸の１５部、２，２’－アゾビス（２－メチルブチロニトリル）の７部からなる混合物を５時間かけて滴下し、滴下終了後も、同温度に１０時間保持して反応を続行した。反応液の温度を５０℃に下げ、ｔ－ブチルピロカテコールの０．２部を酢酸ブチルの１５部に溶解した溶液を加え、さらにグリシジルメタクリレートの１５部、ジメチルアミノエタノールの３０部を加えた後に、８０℃まで昇温し、同温度で１０時間反応を行う事で、非水溶媒に可溶な重合性不飽和基を含有するポリマー（Ｂ－１）の溶液を得た。 Reference Example 1 Synthesis of Polymer (B-1) Containing Polymerizable Unsaturated Group Soluble in Nonaqueous Solvent
A four-necked flask equipped with a thermometer, a stirrer, a reflux condenser and a nitrogen gas inlet tube was charged with 500 parts of heptane and 470 parts of butyl acetate, and the temperature was raised to 90 ° C. A mixture of 985 parts of butyl acid, 15 parts of methacrylic acid and 7 parts of 2,2′-azobis (2-methylbutyronitrile) was added dropwise over 5 hours, and after completion of the addition, the mixture was kept at the same temperature for 10 hours. The reaction was continued with holding. The temperature of the reaction solution was lowered to 50 ° C., a solution in which 0.2 part of t-butylpyrocatechol was dissolved in 15 parts of butyl acetate was added, and 15 parts of glycidyl methacrylate and 30 parts of dimethylaminoethanol were further added. The mixture was heated to 80 ° C. and reacted at the same temperature for 10 hours to obtain a polymer (B-1) solution containing a polymerizable unsaturated group soluble in a non-aqueous solvent.
＜参考例２　非水溶媒に可溶な重合性不飽和基を含有するポリマー（Ｂ－２）の合成＞
　参考例１と同様の反応装置に、ヘプタンの５００部、酢酸ブチルの５００部を仕込んで９０℃に昇温し、同温度に達したところで、アクリル酸ブチルの９５０部、メタクリル酸ジメチルアミノエチルの５０部、２，２’－アゾビス（２－メチルブチロニトリル）の７部からなる混合物を５時間かけて滴下し、滴下終了後も、同温度に１０時間保持して反応を続行した。反応液の温度を５０℃に下げ、ｔ－ブチルピロカテコールの０．２部を酢酸ブチルの２０部に溶解した溶液を加え、さらにグリシジルメタクリレートの２０部を加えた後に、８０℃まで昇温し、同温度で１０時間反応を行う事で、非水溶媒に可溶な重合性不飽和基を含有するポリマー（Ｂ－２）の溶液を得た。 Reference Example 2 Synthesis of Polymer (B-2) Containing Polymerizable Unsaturated Group Soluble in Nonaqueous Solvent
In the same reactor as in Reference Example 1, 500 parts of heptane and 500 parts of butyl acetate were charged and the temperature was raised to 90 ° C. When the same temperature was reached, 950 parts of butyl acrylate and dimethylaminoethyl methacrylate were added. A mixture consisting of 50 parts and 7 parts of 2,2′-azobis (2-methylbutyronitrile) was added dropwise over 5 hours. After completion of the addition, the reaction was continued for 10 hours at the same temperature. The temperature of the reaction solution was lowered to 50 ° C., a solution in which 0.2 part of t-butylpyrocatechol was dissolved in 20 parts of butyl acetate was added, 20 parts of glycidyl methacrylate was further added, and the temperature was raised to 80 ° C. By performing the reaction at the same temperature for 10 hours, a polymer (B-2) solution containing a polymerizable unsaturated group soluble in a non-aqueous solvent was obtained.
＜参考例３　変性顔料（Ｄ－１）の合成＞　
　一次粒子の平均粒子径が０．１～１０μｍのε型銅フタロシアニンブルークルードの２００部、粉砕した塩化ナトリウムの１４００部、ジエチレングリコールの２００部の割合で双腕型ニーダーに仕込み、８０℃～９０℃で１０時間混練した。混練後８０℃の１％塩酸水溶液の２００００部に取り出し、１時間攪拌後、濾過、湯洗を繰り返した後、プレスろ過を行う事により、ε型銅フタロシアニンブルー（Ｃ．Ｉ．Ｐｉｇｍｅｎｔ　Ｂｌｕｅ　１５：６）の顔料成分が４８％のウエットケーキを得た。透過型電子顕微鏡ＪＥＭ－２０１０（日本電子（株）製）で測定した一次粒子の平均粒子径は４０ｎｍであった。
　得られたε型銅フタロシアニンブルーのウエットケーキ（顔料分４８％）の２０８部、参考例１で得られたポリマー（Ｂ－１）の１０部、１．２５ｍｍのジルコニアビーズの６００部、ヘプタンの３００部をポリエチレン広口瓶に入れ、ペイントシェーカー（東洋精機株式会社）で９０分間混合を行った。ヘプタンの３００部で希釈した後、ジルコニアビーズを除去し、顔料混合液を作成した。
　得られた顔料混合液の４００部を温度計、攪拌機、還流冷却器および窒素ガス導入管を備えたセパラブルフラスコに仕込んだ後、重合性単量体（Ｃ）として、メタクリル酸メチルの３．２部およびエチレングリコールジメタクリレートの１．７部の重合性単量体組成物に２，２’－アゾビス（２－メチルブチロニトリル）の１部を溶解したものおよびヘプタンの２００部を加えた。室温で３０分間攪拌を続けた後、８０℃に昇温し、同温度で１５時間反応を続けた。降温後、濾過を行う事で、変性顔料と重合溶剤を分離した。得られた変性顔料を熱風乾燥機により１００℃で５時間乾燥後、粉砕機にて粉砕を行う事で、変性顔料（Ｄ－１）を得た。 <Reference Example 3 Synthesis of Modified Pigment (D-1)>
Charge 200 parts of ε-type copper phthalocyanine blue crude with an average primary particle size of 0.1 to 10 μm, 1400 parts of crushed sodium chloride, and 200 parts of diethylene glycol into a double-arm kneader, 80 ° C. to 90 ° C. And kneading for 10 hours. After kneading, it is taken out into 20000 parts of 1% hydrochloric acid aqueous solution at 80 ° C., stirred for 1 hour, filtered and washed with hot water, and then subjected to press filtration to obtain ε-type copper phthalocyanine blue (CI Pigment Blue 15: A wet cake having a pigment component of 6) of 48% was obtained. The average particle diameter of primary particles measured with a transmission electron microscope JEM-2010 (manufactured by JEOL Ltd.) was 40 nm.
208 parts of the obtained ε-type copper phthalocyanine blue wet cake (pigment content 48%), 10 parts of the polymer (B-1) obtained in Reference Example 1, 600 parts of 1.25 mm zirconia beads, heptane 300 parts were placed in a polyethylene jar and mixed for 90 minutes with a paint shaker (Toyo Seiki Co., Ltd.). After dilution with 300 parts of heptane, the zirconia beads were removed to prepare a pigment mixture.
400 parts of the obtained pigment mixed solution was charged into a separable flask equipped with a thermometer, a stirrer, a reflux condenser, and a nitrogen gas introduction tube, and then methyl methacrylate (3) was used as the polymerizable monomer (C). A polymerizable monomer composition of 2 parts and 1.7 parts of ethylene glycol dimethacrylate dissolved in 1 part of 2,2′-azobis (2-methylbutyronitrile) and 200 parts of heptane were added. . After stirring for 30 minutes at room temperature, the temperature was raised to 80 ° C., and the reaction was continued for 15 hours at the same temperature. After cooling, the modified pigment and the polymerization solvent were separated by filtration. The obtained modified pigment was dried with a hot air dryer at 100 ° C. for 5 hours and then pulverized with a pulverizer to obtain a modified pigment (D-1).
＜参考例４　変性顔料（Ｄ－２）の合成＞　
　参考例３で得たε型銅フタロシアニンブルーのウエットケーキ（顔料分４８％）の２０８部、参考例１で得られたポリマー（Ｂ－１）の１５部、１．２５ｍｍのジルコニアビーズの６００部、ヘプタンの３００部をポリエチレン広口瓶に入れ、ペイントシェーカー（東洋精機株式会社）で９０分間混合を行った。ヘプタンの３００部で希釈した後、ジルコニアビーズを除去し、顔料混合液を作成した。
　得られた顔料混合液の４００部を参考例３と同様の反応装置に仕込んだ後、重合性単量体（Ｃ）として、ｔ－ブチルアクリルアミドスルホン酸の１部を２０部のイオン交換水に溶解したものを加え、さらにメタクリル酸メチルの２．２部およびエチレングリコールジメタクリレートの１．７部の重合性単量体組成物に２，２’－アゾビス（２－メチルブチロニトリル）の１部を溶解したものおよびヘプタンの２００部を加えた。室温で３０分間攪拌を続けた後、８０℃に昇温し、同温度で１５時間反応を続けた。降温後、濾過を行う事で、変性顔料と重合溶剤を分離した。得られた変性顔料を熱風乾燥機により１００℃で５時間乾燥後、粉砕機にて粉砕を行う事で、変性顔料（Ｄ－２）を得た。 <Reference Example 4 Synthesis of Modified Pigment (D-2)>
208 parts of the ε-type copper phthalocyanine blue wet cake (pigment content 48%) obtained in Reference Example 3, 15 parts of the polymer (B-1) obtained in Reference Example 1, 600 parts of 1.25 mm zirconia beads 300 parts of heptane were put into a polyethylene jar and mixed for 90 minutes with a paint shaker (Toyo Seiki Co., Ltd.). After dilution with 300 parts of heptane, the zirconia beads were removed to prepare a pigment mixture.
400 parts of the resulting pigment mixture was charged into the same reaction apparatus as in Reference Example 3, and then 1 part of t-butylacrylamide sulfonic acid as 20 parts of ion-exchanged water was used as the polymerizable monomer (C). The dissolved one is added, and further, 2 parts of 2,2′-azobis (2-methylbutyronitrile) is added to a polymerizable monomer composition of 2.2 parts of methyl methacrylate and 1.7 parts of ethylene glycol dimethacrylate. Dissolved parts and 200 parts of heptane were added. After stirring for 30 minutes at room temperature, the temperature was raised to 80 ° C., and the reaction was continued for 15 hours at the same temperature. After cooling, the modified pigment and the polymerization solvent were separated by filtration. The obtained modified pigment was dried with a hot air dryer at 100 ° C. for 5 hours and then pulverized with a pulverizer to obtain a modified pigment (D-2).
＜参考例５　変性顔料（Ｄ－３）の合成＞
　ファーストゲングリーン２ＹＫ－ＣＦ（大日本インキ化学工業株式会社製ポリハロゲン化銅フタロシアニン顔料、Ｃ．Ｉ．Ｐｉｇｍｅｎｔ　Ｇｒｅｅｎ３６）の１００部、ＡＢ－６（東亜合成株式会社製ポリブチルアクリレートマクロモノマー）の１０部、１．２５ｍｍのジルコニアビーズの６００部、ヘプタンの３００部をポリエチレン広口瓶に入れ、ペイントシェーカー（東洋精機株式会社）で６０分間混合を行った。ヘプタンの４００部で希釈した後、ジルコニアビーズを除去し、顔料混合液を作成した。
　得られた顔料混合液の４００部を参考例３と同様に反応装置に仕込んだ後、重合性単量体（Ｃ）としてｔ－ブチルアクリルアミドスルホン酸の０．８部を２０部のイオン交換水に溶解したものを加え、さらにメタクリル酸メチルの２．４部およびエチレングリコールジメタクリレートの１．７部の重合性単量体組成物に２，２’－アゾビス（２－メチルブチロニトリル）の１部を溶解したものおよびヘプタンの１４０部を加えた。室温で３０分間攪拌を続けた後、８０℃に昇温し、同温度で１５時間反応を続けた。降温後、濾過を行う事で、ポリマー処理顔料と重合溶剤を分離した。得られたポリマー処理顔料を熱風乾燥機により１００℃で５時間乾燥後、粉砕機にて粉砕を行う事で、変性顔料（Ｄ－３）を得た。 <Reference Example 5 Synthesis of Modified Pigment (D-3)>
10 parts of Fastgen Green 2YK-CF (polyhalogenated copper phthalocyanine pigment manufactured by Dainippon Ink & Chemicals, Inc., CI Pigment Green 36), AB-6 (polybutyl acrylate macromonomer manufactured by Toa Gosei Co., Ltd.) Part, 600 parts of 1.25 mm zirconia beads and 300 parts of heptane were placed in a polyethylene jar and mixed for 60 minutes with a paint shaker (Toyo Seiki Co., Ltd.). After dilution with 400 parts of heptane, the zirconia beads were removed to prepare a pigment mixture.
400 parts of the obtained pigment mixed solution was charged into a reaction apparatus in the same manner as in Reference Example 3, and then 0.8 parts of t-butylacrylamidesulfonic acid as a polymerizable monomer (C) was added to 20 parts of ion-exchanged water. In addition, 2.4 parts of methyl methacrylate and 1.7 parts of ethylene glycol dimethacrylate were added to a polymerizable monomer composition of 2,2′-azobis (2-methylbutyronitrile). One part dissolved and 140 parts heptane were added. After stirring for 30 minutes at room temperature, the temperature was raised to 80 ° C., and the reaction was continued for 15 hours at the same temperature. After cooling, the polymer-treated pigment and the polymerization solvent were separated by filtration. The obtained polymer-treated pigment was dried with a hot air dryer at 100 ° C. for 5 hours and then pulverized with a pulverizer to obtain a modified pigment (D-3).
＜参考例６　変性顔料（Ｄ－４）の合成＞
　一次粒子の平均粒子径が０．１～１０μｍのポリ臭素化亜鉛フタロシアニンの２００部、粉砕した塩化ナトリウム２０００部、ジエチレングリコール２００部を双腕型ニーダーに仕込み、１００℃で８時間混練した。混練終了後、６０℃の温水に取り出し、１時間撹拌後、濾過、湯洗を繰り返した後、プレスろ過を行うことにより、ポリ臭素化亜鉛フタロシアニン（Ｃ．Ｉ．Ｐｉｇｍｅｎｔ　Ｇｒｅｅｎ　５８）の顔料成分が４５％のウエットケーキを得た。透過型電子顕微鏡ＪＥＭ－２０１０（日本電子（株）製）で測定した一次粒子の平均粒子径は５０ｎｍであった。
　得られたポリ臭素化亜鉛フタロシアニンのウエットケーキの２２２部、参考例２で得られたポリマー（Ｂ－２）の１０部、１．２５ｍｍのジルコニアビーズの６００部、ヘプタンの３００部をポリエチレン広口瓶に入れ、ペイントシェーカー（東洋精機株式会社）で６０分間混合を行った。ヘプタンの３００部で希釈した後、ジルコニアビーズを除去し、顔料混合液を作成した。
　得られた顔料混合液の４００部を参考例３と同様に反応装置に仕込んだ後、重合性単量体（Ｃ）として、ｔ－ブチルアクリルアミドスルホン酸の１部を２０部のイオン交換水に溶解したものを加え、さらにメタクリル酸メチルの１．９部およびエチレングリコールジメタクリレートの１．９部の重合性単量体組成物に２，２’－アゾビス（２－メチルブチロニトリル）の１部を溶解したものおよびヘプタンの１４０部を加えた。降温後、濾過を行う事で、ポリマー処理顔料と重合溶剤を分離した。得られたポリマー処理顔料を熱風乾燥機により１００℃で５時間乾燥後、粉砕機にて粉砕を行う事で、変性顔料（Ｄ－４）を得た。 <Reference Example 6 Synthesis of Modified Pigment (D-4)>
200 parts of polybrominated zinc phthalocyanine having an average primary particle size of 0.1 to 10 μm, 2000 parts of crushed sodium chloride, and 200 parts of diethylene glycol were charged into a double-arm kneader and kneaded at 100 ° C. for 8 hours. After completion of the kneading, the pigment component of polybrominated zinc phthalocyanine (CI Pigment Green 58) is obtained by taking out into warm water of 60 ° C., stirring for 1 hour, repeating filtration and washing with hot water, and then performing press filtration. A 45% wet cake was obtained. The average particle size of the primary particles measured with a transmission electron microscope JEM-2010 (manufactured by JEOL Ltd.) was 50 nm.
222 parts of the resulting polybrominated zinc phthalocyanine wet cake, 10 parts of the polymer (B-2) obtained in Reference Example 2, 600 parts of 1.25 mm zirconia beads and 300 parts of heptane were placed in a polyethylene jar. And mixed for 60 minutes with a paint shaker (Toyo Seiki Co., Ltd.). After dilution with 300 parts of heptane, the zirconia beads were removed to prepare a pigment mixture.
After 400 parts of the obtained pigment mixed solution was charged into the reactor in the same manner as in Reference Example 3, as a polymerizable monomer (C), 1 part of t-butylacrylamide sulfonic acid was added to 20 parts of ion-exchanged water. In addition, 1.9 parts of methyl methacrylate and 1.9 parts of ethylene glycol dimethacrylate were added to the polymerizable monomer composition, and 1 of 2,2′-azobis (2-methylbutyronitrile) was added. Dissolved parts and 140 parts of heptane were added. After cooling, the polymer-treated pigment and the polymerization solvent were separated by filtration. The obtained polymer-treated pigment was dried with a hot air dryer at 100 ° C. for 5 hours and then pulverized with a pulverizer to obtain a modified pigment (D-4).
＜参考例７　変性顔料（Ｄ－５）の合成＞
　イルガフォア　ＲＥＤ　ＢＴ－ＣＦ（チバスペシャリティーケミカルス社製品）の１００部、参考例２で得られたポリマー（Ｂ－２）の１５部、１．２５ｍｍのジルコニアビーズの６００部、ヘプタンの３００部をポリエチレン広口瓶に入れ、ペイントシェーカー（東洋精機株式会社）で６０分間混合を行った。ヘプタンの４００部で希釈した後、ジルコニアビーズを除去し、顔料混合液を作成した。
　得られた顔料混合液の４００部を参考例３と同様に反応装置に仕込んだ後、重合性単量体（Ｃ）として、スチレンの２．２部およびジビニルベンゼン（成分が５５％で、４５％構造異性体（エチルビニルベンゼン）を含む）の５．２部の重合性単量体組成物に２，２’－アゾビス（２－メチルブチロニトリル）の１．５部を溶解したものおよびヘプタンの１６０部を加えた。室温で３０分間攪拌を続けた後、８０℃に昇温し、同温度で１５時間反応を続けた。降温後、濾過を行う事で、ポリマー処理顔料と重合溶剤を分離した。得られたポリマー処理顔料を熱風乾燥機により１００℃で５時間乾燥後、粉砕機にて粉砕を行う事で、変性顔料（Ｄ－５）を得た。 <Reference Example 7 Synthesis of Modified Pigment (D-5)>
100 parts of Irgaphore RED BT-CF (product of Ciba Specialty Chemicals), 15 parts of polymer (B-2) obtained in Reference Example 2, 600 parts of 1.25 mm zirconia beads, 300 parts of heptane The mixture was placed in a jar and mixed for 60 minutes with a paint shaker (Toyo Seiki Co., Ltd.). After dilution with 400 parts of heptane, the zirconia beads were removed to prepare a pigment mixture.
After charging 400 parts of the obtained pigment mixed liquid into the reaction apparatus in the same manner as in Reference Example 3, as the polymerizable monomer (C), 2.2 parts of styrene and divinylbenzene (the component was 55%, 45% % Of 2,2′-azobis (2-methylbutyronitrile) dissolved in 5.2 parts of polymerizable monomer composition of% structural isomer (including ethyl vinylbenzene) and 160 parts of heptane were added. After stirring for 30 minutes at room temperature, the temperature was raised to 80 ° C., and the reaction was continued for 15 hours at the same temperature. After cooling, the polymer-treated pigment and the polymerization solvent were separated by filtration. The obtained polymer-treated pigment was dried with a hot air dryer at 100 ° C. for 5 hours and then pulverized with a pulverizer to obtain a modified pigment (D-5).
＜参考例８　変性顔料（Ｄ－６）の合成＞
　Ｈｏｓｔａｐｅｒｍ　Ｖｉｏｌｅｔ　ＲＬ－ＮＦ（クラリアント社製品、Ｃ．Ｉ．Ｐｉｇｍｅｎｔ　Ｖｉｏｌｅｔ　２３）の１００部、参考例１で得られたポリマー（Ｂ－１）の２０部、１．２５ｍｍのジルコニアビーズの６００部、ヘプタンの３００部をポリエチレン広口瓶に入れ、ペイントシェーカー（東洋精機株式会社）で６０分間混合を行った。ヘプタンの４００部で希釈した後、ジルコニアビーズを除去し、顔料混合液を作成した。
　得られた顔料混合液の４００部を参考例３と同様に反応装置に仕込んだ後、重合性単量体（Ｃ）として、ｔ－ブチルアクリルアミドスルホン酸の０．８部を２０部のイオン交換水に溶解したものを加え、さらにメタクリル酸メチルの４．３部およびエチレングリコールジメタクリレートの２．２部の重合性単量体組成物に２，２’－アゾビス（２－メチルブチロニトリル）の１．５部を溶解したものおよびヘプタンの１２０部を加えた。室温で３０分間攪拌を続けた後、８０℃に昇温し、同温度で１５時間反応を続けた。降温後、濾過を行う事で、ポリマー処理顔料と重合溶剤を分離した。得られたポリマー処理顔料を熱風乾燥機により１００℃で５時間乾燥後、粉砕機にて粉砕を行う事で、変性顔料（Ｄ－６）を得た。 <Reference Example 8 Synthesis of Modified Pigment (D-6)>
100 parts of Hostaperm Violet RL-NF (Clariant product, CI Pigment Violet 23), 20 parts of polymer (B-1) obtained in Reference Example 1, 600 parts of 1.25 mm zirconia beads, heptane 300 parts of was placed in a polyethylene jar and mixed for 60 minutes with a paint shaker (Toyo Seiki Co., Ltd.). After dilution with 400 parts of heptane, the zirconia beads were removed to prepare a pigment mixture.
400 parts of the obtained pigment mixed solution was charged into the reaction apparatus in the same manner as in Reference Example 3, and then 0.8 parts of t-butylacrylamide sulfonic acid was ion-exchanged as a polymerizable monomer (C). A solution dissolved in water is added, and further 2,2′-azobis (2-methylbutyronitrile) is added to a polymerizable monomer composition of 4.3 parts of methyl methacrylate and 2.2 parts of ethylene glycol dimethacrylate. Of 1.5 parts and 120 parts of heptane were added. After stirring for 30 minutes at room temperature, the temperature was raised to 80 ° C., and the reaction was continued for 15 hours at the same temperature. After cooling, the polymer-treated pigment and the polymerization solvent were separated by filtration. The obtained polymer-treated pigment was dried with a hot air dryer at 100 ° C. for 5 hours and then pulverized with a pulverizer to obtain a modified pigment (D-6).
＜参考例９　変性顔料（Ｄ－７）の合成＞
　Ｙｅｌｌｏｗ　Ｐｉｇｍｅｎｔ　Ｅ４ＧＮ（バイエル社製品、Ｃ．Ｉ．ＰｉｇｍｅｎｔＹｅｌｌｏｗ　１５０）の１００部、参考例２で得られたポリマー（Ｂ－２）の１５部、１．２５ｍｍのジルコニアビーズの６００部、ヘプタンの３００部をポリエチレン広口瓶に入れ、ペイントシェーカー（東洋精機株式会社）で６０分間混合を行った。ヘプタンの４００部で希釈した後、ジルコニアビーズを除去し、顔料混合液を作成した。
　得られた顔料混合液の４００部を参考例３と同様に反応装置に仕込んだ後、重合性単量体（Ｃ）として、ｔ－ブチルアクリルアミドスルホン酸の１部を２０部のイオン交換水に溶解したものを加え、さらにメタクリル酸メチルの３．４部およびエチレングリコールジメタクリレートの２．９部の重合性単量体組成物に２，２’－アゾビス（２－メチルブチロニトリル）の１．５部を溶解したものおよびヘプタンの１５０部を加えた。室温で３０分間攪拌を続けた後、８０℃に昇温し、同温度で１５時間反応を続けた。降温後、濾過を行う事で、ポリマー処理顔料と重合溶剤を分離した。得られたポリマー処理顔料を熱風乾燥機により１００℃で５時間乾燥後、粉砕機にて粉砕を行う事で、変性顔料（Ｄ－７）を得た。 <Reference Example 9 Synthesis of Modified Pigment (D-7)>
100 parts of Yellow Pigment E4GN (Bayer product, CI Pigment Yellow 150), 15 parts of the polymer (B-2) obtained in Reference Example 2, 600 parts of 1.25 mm zirconia beads, 300 parts of heptane Was placed in a polyethylene jar and mixed for 60 minutes with a paint shaker (Toyo Seiki Co., Ltd.). After dilution with 400 parts of heptane, the zirconia beads were removed to prepare a pigment mixture.
After 400 parts of the obtained pigment mixed solution was charged into the reactor in the same manner as in Reference Example 3, as a polymerizable monomer (C), 1 part of t-butylacrylamide sulfonic acid was added to 20 parts of ion-exchanged water. In addition, the dissolved monomer composition was added to a polymerizable monomer composition of 3.4 parts of methyl methacrylate and 2.9 parts of ethylene glycol dimethacrylate, and 1 of 2,2′-azobis (2-methylbutyronitrile) was added. .5 parts dissolved and 150 parts heptane were added. After stirring for 30 minutes at room temperature, the temperature was raised to 80 ° C., and the reaction was continued for 15 hours at the same temperature. After cooling, the polymer-treated pigment and the polymerization solvent were separated by filtration. The obtained polymer-treated pigment was dried with a hot air dryer at 100 ° C. for 5 hours and then pulverized with a pulverizer to obtain a modified pigment (D-7).
＜実施例１＞
　参考例３で得られた変性顔料（Ｄ－１）の９部、分散助剤として銅フタロシアニンモノフタルイミドメチル（フタロシアニン誘導体）０．５部と銅フタロシアニンモノスルホン酸（フタロシアニン誘導体）０．５部、アジスパーＰＢ８１４（味の素ファインテクノ製顔料分散剤、有効成分６０％）の５部、プロピレングリコールモノメチルエーテルアセテート５７．２部、０．３ｍｍφセプルビーズを加え、ペイントコンディショナー（東洋精機株式会社製）で３時間分散した後、０．３ｍｍφセプルビーズを取り除く事で、顔料分散組成物を得た。同顔料分散液の粘度は、東機産業製ＲＥ５５０Ｌ型粘度計で２０℃、１０ｒｐｍの条件で１０ｍＰａ・ｓであった。
　また、４０℃で１週間保存後の粘度は１０ｍＰａ・ｓで変化は無く、顔料の沈降も無い分散安定性の高い顔料分散組成物であった。粘度変化については、±１０％以内の粘度変化を合格とした。 <Example 1>
9 parts of the modified pigment (D-1) obtained in Reference Example 3, 0.5 part of copper phthalocyanine monophthalimidomethyl (phthalocyanine derivative) and 0.5 part of copper phthalocyanine monosulfonic acid (phthalocyanine derivative) as a dispersion aid, Add 5 parts of Azisper PB814 (Ajinomoto Fine Techno Pigment Dispersant, active ingredient 60%), 57.2 parts of propylene glycol monomethyl ether acetate, 0.3 mmφ Sepul beads, and disperse for 3 hours with Paint Conditioner (Toyo Seiki Co., Ltd.) Then, the pigment dispersion composition was obtained by removing 0.3 mmφ sepul beads. The viscosity of the pigment dispersion was 10 mPa · s on a RE550L viscometer manufactured by Toki Sangyo under the conditions of 20 ° C. and 10 rpm.
Moreover, the viscosity after storage for 1 week at 40 ° C. was a pigment dispersion composition having a high dispersion stability with no change at 10 mPa · s and no precipitation of the pigment. About the viscosity change, the viscosity change within ± 10% was regarded as acceptable.
＜実施例２～７＞
　使用する変性顔料（Ｄ－１）、誘導体、溶剤、顔料分散剤を、表１及び表２の記載に変更する以外は実施例１と同様にして、顔料分散組成物を作製し、粘度および保存安定性を評価した。 <Examples 2 to 7>
A pigment dispersion composition was prepared in the same manner as in Example 1 except that the modified pigment (D-1), derivative, solvent, and pigment dispersant used were changed as described in Tables 1 and 2, and the viscosity and storage were prepared. Stability was evaluated.
＜比較例１＞
　ファーストゲングリーン２ＹＫ－ＣＦ（大日本インキ化学工業株式会社製ポリハロゲン化銅フタロシアニン顔料、Ｃ．Ｉ．Ｐｉｇｍｅｎｔ　Ｇｒｅｅｎ３６）（変性顔料（Ｄ－３）で使用している顔料である）の１０部、アジスパーＰＢ８１４（味の素ファインテクノ製顔料分散剤、有効成分６０％）の１０部、プロピレングリコールモノメチルエーテルアセテート５５．２部、０．３ｍｍφセプルビーズを加え、ペイントコンディショナー（東洋精機株式会社製）で３時間分散した後、０．３ｍｍφセプルビーズを取り除く事で、顔料分散組成物を得た。同顔料分散液の粘度は、東機産業製ＲＥ５５０Ｌ型粘度計で２０℃、１０ｒｐｍの条件で１１ｍＰａ・ｓであった。
　しかし、４０℃で１週間保存後の粘度は２４ｍＰａ・ｓで増粘しており、顔料の沈降も観察された。粘度変化については±１０％以内の粘度変化では無いため、不合格とした。 <Comparative Example 1>
10 parts of Fast Gen Green 2YK-CF (Dainippon Ink Chemical Co., Ltd. polyhalogenated copper phthalocyanine pigment, CI Pigment Green 36) (the pigment used in the modified pigment (D-3)), Add 10 parts of Azisper PB814 (Ajinomoto Fine Techno Pigment Dispersant, active ingredient 60%), 55.2 parts of propylene glycol monomethyl ether acetate, 0.3 mmφ Sepul beads, and disperse for 3 hours with Paint Conditioner (Toyo Seiki Co., Ltd.) Then, the pigment dispersion composition was obtained by removing 0.3 mmφ sepul beads. The viscosity of the pigment dispersion was 11 mPa · s using a RE550L viscometer manufactured by Toki Sangyo under the conditions of 20 ° C. and 10 rpm.
However, the viscosity after storage at 40 ° C. for 1 week was increased at 24 mPa · s, and precipitation of the pigment was also observed. The viscosity change was rejected because it was not within ± 10%.
＜比較例２＞
　使用する顔料、溶剤、顔料分散剤を、表２の記載に変更する以外は実施例１と同様にして、顔料分散組成物を作製し、粘度および保存安定性を評価した。 <Comparative example 2>
A pigment dispersion composition was prepared in the same manner as in Example 1 except that the pigment, solvent, and pigment dispersant used were changed to those shown in Table 2, and the viscosity and storage stability were evaluated.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
表１中、
「フタロシアニン誘導体１」は「銅フタロシアニンモノフタルイミドメチル（分散助剤）」であり、
「フタロシアニン誘導体２」は「銅フタロシアニンモノスルホン酸（分散助剤）」であり、
「アジスパーＰＢ８１４」は「味の素ファインテクノ製顔料分散剤、有効成分６０％」だり、
「ＤＩＳＰＥＲＢＹＫ－２００１」は「ＢＹＫ社製顔料分散剤、有効成分４６％」であり、
「ＰＧＭＥＡ」は「プロピレングリコールモノメチルエーテルアセテート」である。 In Table 1,
“Phthalocyanine derivative 1” is “copper phthalocyanine monophthalimidomethyl (dispersing aid)”,
“Phthalocyanine derivative 2” is “copper phthalocyanine monosulfonic acid (dispersion aid)”,
"Azisper PB814" is "Ajinomoto Fine Techno pigment dispersant, active ingredient 60%"
“DISPERBYK-2001” is “pigment dispersant by BYK, active ingredient 46%”,
“PGMEA” is “propylene glycol monomethyl ether acetate”.
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
表２中、
「顔料１」は「ファーストゲングリーン２ＹＫ－ＣＦ（大日本インキ化学工業株式会社製ポリハロゲン化銅フタロシアニン顔料、Ｃ．Ｉ．Ｐｉｇｍｅｎｔ　Ｇｒｅｅｎ３６）」であり、
「顔料２」は「Ｈｏｓｔａｐｅｒｍ　Ｖｉｏｌｅｔ　ＲＬ－ＮＦ（クラリアント社製品、Ｃ．Ｉ．Ｐｉｇｍｅｎｔ　Ｖｉｏｌｅｔ　２３）」であり、
「アジスパーＰＢ８１４」は「味の素ファインテクノ製顔料分散剤、有効成分６０％」であり、
「ＤＩＳＰＥＲＢＹＫ－２００１」は「ＢＹＫ社製顔料分散剤、有効成分４６％」であり、
「ＰＧＭＥＡ」は「プロピレングリコールモノメチルエーテルアセテート」である。 In Table 2,
"Pigment 1" is "Fastgen Green 2YK-CF (Dainippon Ink Chemical Co., Ltd. polyhalogenated copper phthalocyanine pigment, CI Pigment Green 36)"
“Pigment 2” is “Hostaperm Violet RL-NF (product of Clariant, CI Pigment Violet 23)”,
“Azisper PB814” is “Ajinomoto Fine Techno Pigment Dispersant, Active ingredient 60%”
“DISPERBYK-2001” is “pigment dispersant by BYK, active ingredient 46%”,
“PGMEA” is “propylene glycol monomethyl ether acetate”.
　比較例１は、実施例３で使用した変性顔料（Ｄ－３）の未変性の顔料を使用した例であるが、粘度変化が大きく、且つ顔料の沈降も見られた。また、比較例２は、実施例６で使用した変性顔料（Ｄ－６）の未変性の顔料を使用した例であるが、これも粘度変化が大きく、且つ顔料の沈降も見られた。一方、変性顔料（Ｄ－１）～（Ｄ－７）を使用した本発明のカラーフィルター用顔料分散組成物は、使用する顔料の種類に関係なく安定した分散性を示した。 Comparative Example 1 is an example in which the unmodified pigment (D-3) used in Example 3 was used, but the viscosity change was large and the pigment settled. Comparative Example 2 is an example in which the unmodified pigment of the modified pigment (D-6) used in Example 6 was used. This also showed a large change in viscosity, and precipitation of the pigment was also observed. On the other hand, the pigment dispersion composition for color filters of the present invention using the modified pigments (D-1) to (D-7) showed stable dispersibility regardless of the type of pigment used.
＜応用例１　カラーフィルターの製造方法＞
　実施例２で得られた顔料分散組成物の７５部とポリエステルアクリレート樹脂（アロニックス（商標名）Ｍ７１００、東亜合成化学工業株式会社製）５．５部、ジぺンタエリスレートヘキサアクリレート（ＫＡＹＡＲＡＤ（商標名）　ＤＰＨＡ、日本化薬株式会社製）５部、ベンゾフェノン（ＫＡＹＡＣＵＲＥ（商標名）　ＢＰ－１００、日本化薬株式会社製）１部、ユーカーエステルＥＦＰ１３．５部を分散攪拌機で攪拌し、孔径１．０μｍのフィルターで濾過し、カラーレジストを得た。カラーレジストは１ｍｍ厚ガラスに乾燥膜厚１μｍとなるようにスピンコーターを用いて塗布し、その後６０℃で５分間予備乾燥して塗膜を形成させた。紫外線による露光を行った後、２３０℃で１５分間加熱処理して塗膜を硬化させ、カラーフィルターとした。
コントラストは、カラーフィルターを２枚の偏光板の間に設置し、一方には光源を、更にその反対側にはＣＣＤカメラを設置して輝度の測定を行い、偏光軸が平行になる時と垂直になる時との輝度（透過光強度）の比より算出した。この結果、得られたカラーフィルターのコントラストは５９００であった。 <Application Example 1 Color Filter Manufacturing Method>
75 parts of the pigment dispersion composition obtained in Example 2, 5.5 parts of polyester acrylate resin (Aronix (trade name) M7100, manufactured by Toa Gosei Chemical Co., Ltd.), dipentaerythrate hexaacrylate (KAYARAD (trademark) Name) DPHA (made by Nippon Kayaku Co., Ltd.) 5 parts, benzophenone (KAYACURE (trade name) BP-100, made by Nippon Kayaku Co., Ltd.) 1 part, Euker ester EFP 13.5 parts are stirred with a dispersion stirrer, and the pore size is 1 Filtration through a 0.0 μm filter gave a color resist. The color resist was applied to 1 mm thick glass using a spin coater so as to have a dry film thickness of 1 μm, and then preliminarily dried at 60 ° C. for 5 minutes to form a coating film. After exposure with ultraviolet rays, the coating film was cured by heat treatment at 230 ° C. for 15 minutes to obtain a color filter.
Contrast is measured when the color filter is installed between two polarizing plates, a light source is installed on one side, and a CCD camera is installed on the other side. It was calculated from the ratio of brightness (transmitted light intensity) to time. As a result, the contrast of the obtained color filter was 5900.
＜応用例２＞
　実施例４で得られた顔料分散組成物の７５部とポリエステルアクリレート樹脂（アロニックス（商標名）Ｍ７１００、東亜合成化学工業株式会社製）５．５部、ジぺンタエリスレートヘキサアクリレート（ＫＡＹＡＲＡＤ（商標名）　ＤＰＨＡ、日本化薬株式会社製）５部、ベンゾフェノン（ＫＡＹＡＣＵＲＥ（商標名）　ＢＰ－１００、日本化薬株式会社製）１部、ユーカーエステルＥＦＰ１３．５部を分散攪拌機で攪拌し、孔径１．０μｍのフィルターで濾過し、カラーレジストを得た。カラーレジストは１ｍｍ厚ガラスに乾燥膜厚１μｍとなるようにスピンコーターを用いて塗布し、その後６０℃で５分間予備乾燥して塗膜を形成させた。紫外線による露光を行った後、２３０℃で１５分間加熱処理して塗膜を硬化させ、カラーフィルターとした。
得られたカラーフィルターのコントラストを応用例１と同様の測定を行った結果、８８００であった。 <Application example 2>
75 parts of the pigment dispersion composition obtained in Example 4, 5.5 parts of a polyester acrylate resin (Aronix (trade name) M7100, manufactured by Toa Gosei Chemical Co., Ltd.), dipentaerythrate hexaacrylate (KAYARAD (trademark) Name) DPHA (made by Nippon Kayaku Co., Ltd.) 5 parts, benzophenone (KAYACURE (trade name) BP-100, made by Nippon Kayaku Co., Ltd.) 1 part, Euker ester EFP 13.5 parts are stirred with a dispersion stirrer, and the pore size is 1 Filtration through a 0.0 μm filter gave a color resist. The color resist was applied to 1 mm thick glass using a spin coater so as to have a dry film thickness of 1 μm, and then preliminarily dried at 60 ° C. for 5 minutes to form a coating film. After exposure with ultraviolet rays, the coating film was cured by heat treatment at 230 ° C. for 15 minutes to obtain a color filter.
As a result of measuring the contrast of the obtained color filter in the same manner as in Application Example 1, it was 8800.
本発明でカラーフィルター用顔料分散組成物は安定性が高く、これらを用いて作製したカラーフィルターは高いコントラストを示しており、高性能なカラーフィルターの製造に使用が可能である。
また、本発明のカラーフィルター用顔料分散組成物は、カラーフィルター以外にも、例えば印刷インキ、塗料、着色樹脂成型品、静電荷像現像用トナー、インクジェット記録用インキ等の用途にも使用出来る。 In the present invention, the pigment dispersion composition for a color filter has high stability, and a color filter produced using these has a high contrast and can be used for production of a high-performance color filter.
In addition to the color filter, the pigment dispersion composition for a color filter of the present invention can be used for applications such as printing ink, paint, colored resin molded product, electrostatic charge image developing toner, ink jet recording ink and the like.

Claims (3)

  1. 色剤と樹脂と該樹脂を溶解し得る有機溶剤とを含有するカラーフィルター用顔料分散組成物であって、色剤として、顔料（Ａ）表面に、非水溶媒に可溶な重合性不飽和基を含有するポリマー（Ｂ）と非水溶媒に可溶でありかつ重合後に不溶もしくは難溶になる少なくとも１種の重合性不飽和単量体（Ｃ）とを重合することにより得られるポリマー（Ｐ）を有する変性顔料（Ｄ）を含有することを特徴とするカラーフィルター用顔料分散組成物。 A pigment dispersion composition for a color filter, comprising a colorant, a resin, and an organic solvent capable of dissolving the resin, wherein the polymerizable unsaturated as a colorant is soluble in a non-aqueous solvent on the surface of the pigment (A) A polymer obtained by polymerizing a group-containing polymer (B) and at least one polymerizable unsaturated monomer (C) which is soluble in a non-aqueous solvent and becomes insoluble or hardly soluble after polymerization ( A pigment dispersion composition for color filters, comprising a modified pigment (D) having P).
  2. 色剤と樹脂と該樹脂を溶解し得る有機溶剤とを含有するカラーフィルター用顔料分散組成物であって、色剤として、顔料(Ａ)、非水溶媒及び非水溶媒に可溶な重合性不飽和基を含有するポリマー（Ｂ）の存在下で、該非水溶媒に可溶でありかつ重合後に不溶もしくは難溶になる少なくとも１種の重合性不飽和単量体（Ｃ）を重合させた変性顔料（Ｄ）を含有することを特徴とするカラーフィルター用顔料分散組成物。 A pigment dispersion composition for a color filter comprising a colorant, a resin, and an organic solvent capable of dissolving the resin, wherein the colorant has a polymerizable property that is soluble in the pigment (A), the nonaqueous solvent, and the nonaqueous solvent. In the presence of the polymer (B) containing an unsaturated group, at least one polymerizable unsaturated monomer (C) that is soluble in the non-aqueous solvent and insoluble or hardly soluble after polymerization was polymerized. A pigment dispersion composition for color filters, comprising a modified pigment (D).
  3. 前記非水溶媒が脂肪族炭化水素系溶剤及び／又は脂環式炭化水素系溶剤を含む、請求項１～２に記載のカラーフィルター用顔料分散組成物。 The pigment dispersion composition for a color filter according to claim 1 or 2, wherein the non-aqueous solvent includes an aliphatic hydrocarbon solvent and / or an alicyclic hydrocarbon solvent.
PCT/JP2009/055584 2008-03-28 2009-03-23 Pigment dispersing composition for color filters WO2009119473A1 (en)

Priority Applications (4)

Application Number Priority Date Filing Date Title
EP09726089.7A EP2209025A4 (en) 2008-03-28 2009-03-23 PIGMENT DISPERSION COMPOSITION FOR COLOR FILTERS
CN2009801003485A CN101802660B (en) 2008-03-28 2009-03-23 Pigment dispersing composition for color filters
JP2009529445A JP4423575B2 (en) 2008-03-28 2009-03-23 Pigment dispersion composition for color filter
US12/734,567 US8268200B2 (en) 2008-03-28 2009-03-23 Pigment dispersing composition for color filter

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2008086288 2008-03-28
JP2008-086288 2008-03-28

Publications (1)

Publication Number Publication Date
WO2009119473A1 true WO2009119473A1 (en) 2009-10-01

Family

ID=41113666

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2009/055584 WO2009119473A1 (en) 2008-03-28 2009-03-23 Pigment dispersing composition for color filters

Country Status (6)

Country Link
US (1) US8268200B2 (en)
EP (1) EP2209025A4 (en)
JP (1) JP4423575B2 (en)
KR (1) KR101065287B1 (en)
CN (1) CN101802660B (en)
WO (1) WO2009119473A1 (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4687835B2 (en) * 2009-09-09 2011-05-25 Ｄｉｃ株式会社 Pigment dispersion composition for color filter and color filter
JP2012031276A (en) * 2010-07-30 2012-02-16 Dic Corp Pigment dispersion composition for color filter, and color filter

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9187578B2 (en) * 2009-04-16 2015-11-17 Dic Corporation Polymer modified pigment and production process of the same
CN103781858A (en) * 2011-09-09 2014-05-07 Dic株式会社 Composite pigment and method for producing same
CN102504622B (en) * 2011-11-04 2014-01-15 湖北鼎龙化学股份有限公司 Modified pigment and its preparation method and application and nano pigment dispersion
CN102532939B (en) * 2011-12-16 2014-11-12 江南大学 Preparation method of water-based self-dispersion nano organic pigment powder
WO2020009911A1 (en) * 2018-07-02 2020-01-09 Nanotek Instruments, Inc. Dark-color polymer composite films
US11242443B2 (en) 2018-07-02 2022-02-08 Global Graphene Group, Inc. Dark-color polymer composite films
US11186704B2 (en) 2018-07-02 2021-11-30 Global Graphene Group, Inc. Manufacturing process for dark-color polymer composite films

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6140370A (en) * 1984-07-31 1986-02-26 Ricoh Co Ltd Pigment-resin composition and electrophotographic liquid developer using same
JP2000351916A (en) * 1999-06-14 2000-12-19 Dainippon Ink & Chem Inc Pigment dispersion apparatus and pigment dispersion method
JP2003064293A (en) 2001-08-29 2003-03-05 Dainippon Ink & Chem Inc Pigment dispersion composition for color filter, pigment dispersion resist, and color filter
JP2006022164A (en) * 2004-07-06 2006-01-26 Sakata Corp Pigment dispersion composition, use thereof and compound for pigment treatment
JP2006111752A (en) 2004-10-15 2006-04-27 Dainippon Ink & Chem Inc Pigment dispersion composition for color filter and method for producing the same, and method for producing pigment dispersion for color filter
JP2006267283A (en) 2005-03-22 2006-10-05 Fuji Xerox Co Ltd Image forming apparatus
JP2008088211A (en) * 2006-09-29 2008-04-17 Dainippon Ink & Chem Inc Polymer-coated pigment and method for producing the same
JP2008111019A (en) * 2006-10-30 2008-05-15 Dainichiseika Color & Chem Mfg Co Ltd Pigment composition, method for producing the same, colored composition for color filter and color filter
JP2008239869A (en) * 2007-03-28 2008-10-09 Dic Corp Polymer-coated pigment and method for producing the same

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3876603A (en) * 1970-06-22 1975-04-08 Ppg Industries Inc Method of encapsulating pigments in organic dispersions of polymers
CA2352155A1 (en) * 1998-12-31 2000-07-13 Ciba Specialty Chemicals Holding Inc. Pigment composition containing atrp polymers
US7008977B2 (en) * 2001-06-29 2006-03-07 Canon Kabushiki Kaisha Colored fine resin particles and production process thereof, aqueous dispersion of colored fine resin particles and production process of aqueous dispersion of colored fine resin particles, ink , ink cartridge, recording unit, ink-jet recording apparatus, and ink-jet recording process
TW593563B (en) * 2002-01-29 2004-06-21 Toyo Ink Mfg Co Colored composition for color filters and color filter
JP2004035592A (en) * 2002-06-28 2004-02-05 Fuji Photo Film Co Ltd Production method for oily ink composition for inkjet printer, liquid developer for electrophotography, and colored resin particle

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6140370A (en) * 1984-07-31 1986-02-26 Ricoh Co Ltd Pigment-resin composition and electrophotographic liquid developer using same
JP2000351916A (en) * 1999-06-14 2000-12-19 Dainippon Ink & Chem Inc Pigment dispersion apparatus and pigment dispersion method
JP2003064293A (en) 2001-08-29 2003-03-05 Dainippon Ink & Chem Inc Pigment dispersion composition for color filter, pigment dispersion resist, and color filter
JP2006022164A (en) * 2004-07-06 2006-01-26 Sakata Corp Pigment dispersion composition, use thereof and compound for pigment treatment
JP2006111752A (en) 2004-10-15 2006-04-27 Dainippon Ink & Chem Inc Pigment dispersion composition for color filter and method for producing the same, and method for producing pigment dispersion for color filter
JP2006267283A (en) 2005-03-22 2006-10-05 Fuji Xerox Co Ltd Image forming apparatus
JP2008088211A (en) * 2006-09-29 2008-04-17 Dainippon Ink & Chem Inc Polymer-coated pigment and method for producing the same
JP2008111019A (en) * 2006-10-30 2008-05-15 Dainichiseika Color & Chem Mfg Co Ltd Pigment composition, method for producing the same, colored composition for color filter and color filter
JP2008239869A (en) * 2007-03-28 2008-10-09 Dic Corp Polymer-coated pigment and method for producing the same

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of EP2209025A4 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4687835B2 (en) * 2009-09-09 2011-05-25 Ｄｉｃ株式会社 Pigment dispersion composition for color filter and color filter
JP2012031276A (en) * 2010-07-30 2012-02-16 Dic Corp Pigment dispersion composition for color filter, and color filter

Also Published As

Publication number Publication date
EP2209025A4 (en) 2014-02-26
US20100308284A1 (en) 2010-12-09
EP2209025A1 (en) 2010-07-21
US8268200B2 (en) 2012-09-18
CN101802660A (en) 2010-08-11
KR101065287B1 (en) 2011-09-19
CN101802660B (en) 2012-07-18
JP4423575B2 (en) 2010-03-03
KR20100021514A (en) 2010-02-24
JPWO2009119473A1 (en) 2011-07-21

Similar Documents

Publication Publication Date Title
JP4423575B2 (en) Pigment dispersion composition for color filter
AU2010361883B2 (en) Pigment dispersion, production method thereof, photosensitive colored resin composition, inkjet ink and electrophotographic printing toner containing said pigment dispersion, and color filter
JP4717767B2 (en) Pigment dispersion composition
JP4064681B2 (en) Pigment dispersant, pigment dispersion composition containing the same, and colored photosensitive composition
JP2003026950A (en) Pigment dispersing agent, pigment dispersed composition containing this, and coloring photosensitive composition
JP5444760B2 (en) Coloring composition for color filter and color filter
WO2010101210A1 (en) Pigment dispersion composition
JP5834389B2 (en) Resin composition for color filter, color filter, and liquid crystal display device
JP6373813B2 (en) Color filter colorant composition and method for producing pigment dispersant
JP2008088211A (en) Polymer-coated pigment and method for producing the same
JP7415342B2 (en) Photosensitive coloring composition, color filter and liquid crystal display device using the same
JP5622018B2 (en) Modified pigment, pigment dispersion composition and color filter
JP4687835B2 (en) Pigment dispersion composition for color filter and color filter
JP2012078409A (en) Blue pigment dispersion liquid for color filter, blue photosensitive resin composition for color filter, color filter, and liquid crystal display device
JP7525295B2 (en) Pigment dispersion composition for black matrix, resist composition for black matrix, and black matrix
JP2012031276A (en) Pigment dispersion composition for color filter, and color filter
JP5822015B2 (en) Method for producing resin composition for color filter, method for producing color filter
JP2005106859A (en) Resin composition, photosensitive resin composition using the same, photosensitive resin composition for photolithographic spacer and method for manufacturing the same
JP2001335717A (en) Pigment dispersion composition and colored photosensitive composition
JP7507006B2 (en) Pigment dispersion composition for black matrix, resist composition for black matrix, and black matrix
JP2006225431A (en) Carbodiimide compound and method for producing pigment dispersion composition using the same
CN114539847A (en) Pigment dispersion composition for black matrix, resist composition for black matrix, and black matrix
JPH09309904A (en) Manufacture of carbon black grafted polymer

Legal Events

Date Code Title Description
WWE Wipo information: entry into national phase

Ref document number: 200980100348.5

Country of ref document: CN

WWE Wipo information: entry into national phase

Ref document number: 2009529445

Country of ref document: JP

121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 09726089

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 20107000110

Country of ref document: KR

Kind code of ref document: A

WWE Wipo information: entry into national phase

Ref document number: 2009726089

Country of ref document: EP

WWE Wipo information: entry into national phase

Ref document number: 12734567

Country of ref document: US

NENP Non-entry into the national phase

Ref country code: DE

点击 这是indexloc提供的php浏览器服务，不要输入任何密码和下载